Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing mixed homogeneous catalyst formulations

ABSTRACT

A continuous solution polymerization process is disclosed wherein at least two homogeneous catalyst formulations are employed. A first homogeneous catalyst formulation is employed in a first reactor to produce a first ethylene interpolymer and a second homogeneous catalyst formulation is employed in a second reactor to produce a second ethylene interpolymer. Optionally a third ethylene interpolymer is formed in a third reactor. The resulting ethylene interpolymer products possess desirable properties in a variety of end use applications, for example in film applications. A means for increasing the molecular weight of the first ethylene interpolymer is disclosed and/or a means for increasing the temperature of the first reactor, relative to the third homogeneous catalyst formulation. A means for reducing the (α-olefin/ethylene) weight ratio in the first reactor is disclosed and/or reducing the density of the first ethylene interpolymer, relative to the third homogeneous catalyst formulation.

CROSS REFERENCE TO RELATED PATENT APPLICATION

This application is a continuation of U.S. application Ser. No. 15/491,330, filed on Apr. 19, 2017, now issued as U.S. Pat. No. 10,442,921. The contents of U.S. application Ser. No. 15/491,330 are incorporated by reference in their entirety.

BACKGROUND

Solution polymerization processes are typically carried out at temperatures that are above the melting point of the ethylene homopolymer or copolymer product. In a typical solution polymerization process, catalyst components, solvent, monomers and hydrogen are fed under pressure to one or more reactors.

For ethylene polymerization, or ethylene copolymerization, reactor temperatures can range from about 80° C. to about 300° C. while pressures generally range from about 3 MPag to about 45 MPag. The ethylene homopolymer or copolymer produced remains dissolved in the solvent under reactor conditions. The residence time of the solvent in the reactor is relatively short, for example, from about 1 second to about 20 minutes. The solution process can be operated under a wide range of process conditions that allow the production of a wide variety of ethylene polymers. Post reactor, the polymerization reaction is quenched to prevent further polymerization, by adding a catalyst deactivator. Optionally, if a heterogeneous catalyst formulation is employed in the third reactor, the deactivated solution is passivated, by adding an acid scavenger. The deactivated solution, or optionally the passivated solution, is then forwarded to polymer recovery where the ethylene homopolymer or copolymer is separated from process solvent, unreacted residual ethylene and unreacted optional α-olefin(s).

There is a need to improve the continuous solution polymerization process, for example, to increase the molecular weight of the ethylene interpolymer produced at a given reactor temperature. Given a specific catalyst formulation, it is well known to those of ordinary experience that polymer molecular weight increases as reactor temperature decreases. However, decreasing reactor temperature can be problematic when the viscosity of the solution becomes too high. As a result, in the solution polymerization process there is a need for catalyst formulations that produce high molecular weight ethylene interpolymers at high reactor temperatures. The catalyst formulations and solution polymerization processes disclosed herein satisfy this need.

In the solution polymerization process there is also a need for catalyst formulations that are very efficient at incorporating one or more α-olefins into a propagating macromolecular chain. In other words, at a given [α-olefin/ethylene] weight ratio in a solution polymerization reactor, there is a need for catalyst formulations that produce lower density ethylene/α-olefin copolymers. Expressed alternatively, there is a need for catalyst formulations that produce an ethylene/α-olefin copolymer, having a specific density, at a lower (α-olefin/ethylene) ratio in the reactor feed. Such catalyst formulations efficiently utilize the available α-olefin and reduce the amount of α-olefin in solution process recycle streams.

The catalyst formulations and solution process disclosed herein, produce unique ethylene interpolymer products that have desirable properties in a variety of end use applications, for example applications that employ ethylene interpolymer films. Non-limiting examples of desirable film properties include higher film stiffness, higher film tensile yield, higher film tear resistance, lower hexane extractables, lower seal initiation temperature and improved hot tack performance. Films prepared from the ethylene interpolymer products, disclosed herein, have these desirable properties.

SUMMARY OF DISCLOSURE

One embodiment of this disclosure is an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer, and; (iii) optionally a third ethylene interpolymer: where the ethylene interpolymer product has a dimensionless Long Chain Branching Factor (LCBF) greater than or equal to about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium, and; from about 0.006 ppm to about 5.7 ppm of titanium.

Additional embodiments of this disclosure include ethylene interpolymer products comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer, and; (iii) optionally a third ethylene interpolymer: where the ethylene interpolymer product has a dimensionless Long Chain Branching Factor (LCBF) greater than or equal to about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; from about 0.006 ppm to about 5.7 ppm of titanium, and; less than or equal to about 0.01 terminal vinyl unsaturations per 100 carbon atoms.

Additional embodiments of this disclosure include ethylene interpolymer products comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer, and; (iii) optionally a third ethylene interpolymer: where the ethylene interpolymer product has a dimensionless Long Chain Branching Factor (LCBF) greater than or equal to about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; from about 0.006 ppm to about 5.7 ppm of titanium and; from about 0.03 ppm to about 6.0 ppm of total catalytic metal.

Further embodiments of this disclosure include ethylene interpolymer products comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer, and; (iii) optionally a third ethylene interpolymer: where the ethylene interpolymer product has a dimensionless Long Chain Branching Factor (LCBF) greater than or equal to about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; from about 0.006 ppm to about 5.7 ppm of titanium; less than or equal to about 0.01 terminal vinyl unsaturations per 100 carbon atoms, and; from about 0.03 ppm to about 6.0 ppm of total catalytic metal.

Embodiment of this disclosure include ethylene interpolymer products comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer, and; (iii) optionally a third ethylene interpolymer: where the ethylene interpolymer product has a dimensionless Long Chain Branching Factor (LCBF) greater than or equal to about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; from about 0.006 ppm to about 5.7 ppm of titanium; less than or equal to about 0.01 terminal vinyl unsaturations per 100 carbon atoms, and; from about 0.03 ppm to about 6.0 ppm of total catalytic metal.

Embodiments of this disclosure include ethylene interpolymer products having a melt index from about 0.3 to about 500 dg/minute. Further embodiments include ethylene interpolymer products having a density from about 0.855 to about 0.975 g/cc. Other embodiments include ethylene interpolymer products having a M_(w)/M_(n) from about 1.7 to about 25. Embodiments include ethylene interpolymer products having a CDBI₅₀ (Composition Distribution Breadth Index) from about 1% to about 98%.

Embodiments include ethylene interpolymer products containing 5 to 60 wt % of a first ethylene interpolymer, 20 to 95 wt % of a second ethylene interpolymer and 0 to 30 wt % of a third ethylene interpolymer; where wt % is the weight of the first, the second or the optional third ethylene interpolymer, individually, divided by the total weight of the ethylene interpolymer product. Additional embodiments include ethylene interpolymer products where the first ethylene interpolymer has a melt index from about 0.01 to about 200 dg/minute, the second ethylene interpolymer has melt index from about 0.3 to about 1000 dg/minute, and the third ethylene interpolymer has a melt index from about 0.5 to about 2000 dg/minute. Other embodiments include ethylene interpolymer products where the first ethylene interpolymer has a density from about 0.855 g/cm³ to about 0.975 g/cc, the second ethylene interpolymer has a density from about 0.855 g/cm³ to about 0.975 g/cc, and the third ethylene interpolymer has density from about 0.855 g/cm³to about 0.975 g/cc.

Embodiments include ethylene interpolymer products containing from 0 to 10 mole percent of one or more α-olefin, where the α-olefins are C₃ to C₁₀ α-olefins. Non-limiting examples include ethylene interpolymer products containing the following α-olefins: 1-octene, 1-hexene or a mixture of 1-octene and 1-hexene.

Embodiments of this disclosure include a first ethylene interpolymer synthesized using at least one homogeneous catalyst formulation. Additional embodiments include the synthesis of a first ethylene interpolymer using a first homogeneous catalyst formulation. One non-limiting example of the first homogeneous catalyst formulation is a bridged metallocene catalyst formulation containing a component A defined by Formula (I)

Embodiments of this disclosure include a second ethylene interpolymer synthesized using a second homogeneous catalyst formulation. Non-limiting examples of the second homogeneous catalyst formulation include an unbridged single site catalyst formulation.

Optional embodiments include the synthesis of a third ethylene interpolymer using a heterogeneous catalyst formulation. Further optional embodiments include the synthesis of the third ethylene interpolymer using a fifth homogeneous catalyst formulation. The fifth homogeneous catalyst formulation may be: a bridged metallocene catalyst formulation, an unbridged single site catalyst formulation or a fourth homogeneous catalyst formulation. The fourth homogeneous catalyst formulation contains a bulky ligand-metal complex that is not a member of the chemical genera that defines: a) the bulky ligand-metal complex employed in the bridged metallocene catalyst formulation, and; b) the bulky ligand-metal complex employed in the unbridged single site catalyst formulation.

Embodiments of this disclosure include ethylene interpolymer products containing a catalytic metal A that may range from about 2.4 ppm to about 0.0015 ppm, where catalytic metal A originates from the first homogeneous catalyst formulation. Ethylene interpolymer products may also contain a catalytic metal C that may range from about 2.9 ppm to about 0.006 ppm, where catalytic metal C originates from the second homogeneous catalyst formulation. Non-limiting examples of metals A and C include titanium, zirconium and hafnium. Optionally, ethylene interpolymer products may contain a metal D that may range from 0.9 ppm to 0 ppm; where catalytic metal D originates from the fourth homogeneous catalyst formulation. Non-limiting examples of metal D include titanium, zirconium and hafnium. Additional optional embodiments include ethylene interpolymer products that contain a catalytic metal Z that may range from about 3.9 ppm to about 0 ppm; where catalytic metal Z originates from a heterogeneous catalyst formulation. Non-limiting examples of catalytic metal Z includes: titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium or osmium.

Embodiments of the disclosed ethylene interpolymer products contain a first ethylene interpolymer having a first M_(w)/M_(n) from about 1.7 to about 2.8, a second ethylene interpolymer having a second M_(w)/M_(n) from about 1.7 to about 2.8 and an optional third ethylene interpolymer having a third M_(w)/M_(n) from about 1.7 to about 5.0.

Further embodiments of the ethylene interpolymer products contain a first ethylene interpolymer having a first CDBI₅₀ from about 70 to about 98%, a second ethylene interpolymer having a second CDBI₅₀ from about 70 to about 98% and an optional third ethylene interpolymer having a third CDBI₅₀ from about 35 to about 98%. This disclosure includes embodiment of a continuous solution polymerization process where a first and a second reactor are operated in series mode (i.e. the effluent from the first reactor flows into the second reactor), a first homogeneous catalyst formulation is employed in the first reactor and a second homogeneous catalyst formulations is employed in the second reactor; optionally a heterogeneous catalyst formulation or a fifth homogeneous catalyst formulation is employed in an optional third reactor. This embodiment of a continuous solution polymerization process comprises: i) injecting ethylene, a process solvent, a first homogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen into a first reactor to produce a first exit stream containing a first ethylene interpolymer in process solvent; ii) passing the first exit stream into a second reactor and injecting into the second reactor, ethylene, process solvent, a second homogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen to produce a second exit stream containing a second ethylene interpolymer and the first ethylene interpolymer in process solvent; iii) passing the second exit stream into a third reactor and optionally injecting into the third reactor, ethylene, process solvent, one or more α-olefins, hydrogen and a fifth homogeneous catalyst formulation and/or a heterogeneous catalyst formulation to produce a third exit stream containing an optional third ethylene interpolymer, the second ethylene interpolymer and the first ethylene interpolymer in process solvent; iv) phase separating the third exit stream to recover an ethylene interpolymer product comprising the first ethylene interpolymer, the second ethylene interpolymer and the optional third ethylene interpolymer. The solution process, series mode embodiments, were improved by having a lower [α-olefin/ethylene] weight ratio in the first reactor and/or the first reactor produces a higher molecular first ethylene interpolymer. In some embodiments, the disclosed solution process had at least an 70% improved (reduced) [α-olefin/ethylene] weight ratio as defined by the following formula

${\%\mspace{14mu}{{Reduced}\mspace{14mu}\left\lbrack \frac{\alpha - {olefin}}{ethylene} \right\rbrack}} = {{100 \times \left\{ \frac{\left( \frac{\alpha - {olefin}}{ethylene} \right)^{A} - \left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}}{\left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}} \right\}} \leq {{- 70}\%}}$ where (α-olefin/ethylene)^(A) was calculated by dividing the weight of α-olefin added to the first reactor by the weight of ethylene added to the first reactor where a first ethylene interpolymer having a target density was produced by the first homogeneous catalyst formulation, and; (α-olefin/ethylene)^(C) was calculated by dividing the weight of α-olefin added to the first reactor by the weight of ethylene added to the first reactor where a control ethylene interpolymer having the target density was produced by replacing the first homogeneous catalyst formulation with a third homogeneous catalyst formulation. In other embodiments of the solution polymerization process had at least a 5% improved weight average molecular weight as defined by the following formula % Improved M _(w)=100%×(M _(w) ^(A) −M _(w) ^(C))/M _(w) ^(C)≥5% where M_(w) ^(A) was the weight average molecular weight of the first ethylene interpolymer and M_(w) ^(C) was the weight average molecular weight of a comparative ethylene interpolymer; where the comparative ethylene interpolymer was produced in the first reactor by replacing the first homogeneous catalyst formulation with the third homogeneous catalyst formulation.

In another embodiment of the continuous solution polymerization process the first and second reactors are operated in parallel mode, i.e. the first exit stream (exiting the first reactor) by-passes the second reactor and the first exit stream is combined with the second exit stream (exiting the second reactor) downstream of the second reactor. Parallel mode embodiments comprises: i) injecting ethylene, a process solvent, a first homogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen into a first reactor to produce a first exit stream containing a first ethylene interpolymer in process solvent; ii) injecting ethylene, process solvent, a second homogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen into a second reactor to produce a second exit stream containing a second ethylene interpolymer in process solvent; iii) combining the first and second exit streams to form a third exit stream; iv) passing the third exit stream into a third reactor and optionally injecting into the third reactor, ethylene, process solvent, one or more α-olefins, hydrogen and a fifth homogeneous catalyst formulation and/or a heterogeneous catalyst formulation to produce a fourth exit stream containing an optional third ethylene interpolymer, the second ethylene interpolymer and the first ethylene interpolymer in said process solvent; v) phase separating the fourth exit stream to recover an ethylene interpolymer product comprising the first ethylene interpolymer, the second ethylene interpolymer and the optional third ethylene interpolymer. Parallel mode embodiment were improved by having a lower [α-olefin/ethylene] weight ratio in the first reactor and/or a higher molecular first ethylene interpolymer, as characterized by the series mode embodiments described immediately above.

Additional embodiments of the series and parallel solution polymerization processes include the post reactor addition of a catalyst deactivator to neutralize or deactivate the catalysts, forming a deactivated solution. If a heterogeneous catalyst formulation was employed in the third reactor, the continuous solution polymerization process included an additional step where a passivator was added to the deactivated solution, forming a passivated solution. Additional embodiments included steps where the catalyst inlet temperature was adjusted to optimize the activity of the bridged metallocene catalyst formulation.

The disclosed solution polymerization processes include embodiments where the heterogeneous catalyst formulation was a Ziegler-Natta catalyst formulation prepared using an in-line process, hereinafter ‘the in-line Ziegler-Natta catalyst formulation’. In alternative embodiments the heterogeneous catalyst formulation was a Ziegler-Natta catalyst formulation prepared using a batch process, hereinafter ‘the batch Ziegler-Natta catalyst formulation’.

Further embodiments include the solution process synthesis of an ethylene interpolymer product that includes a means for reducing, by at least −70%, the [α-olefin/ethylene] weight ratio required to produce the first ethylene interpolymer (in the ethylene interpolymer product), where the first ethylene interpolymer has a target density; the means involves the appropriate selection of the catalyst formulation employed in the first reactor.

Further embodiments include the synthesis of a solution process ethylene interpolymer product that includes a means for increasing, by at least 5%, the weight average molecular weight (M_(w)) of the first ethylene interpolymer (in the ethylene interpolymer product); the means involves the appropriate selection of the catalyst formulation employed in the first reactor.

Further embodiments of the present disclosure include manufactured articles; non-limiting examples of manufactured articles include flexible articles such as films and rigid articles such a containers.

Manufactured articles embodiments include a polyethylene film comprising at least one layer, where the layer comprises at least one of the ethylene interpolymer products disclosed herein. Such films had a machine direction 1% secant modulus that was improved (by at least 25%) and a transverse direction 1% secant modulus that was improved (by at least 50% higher); relative to a comparative polyethylene film of the same composition but the first ethylene interpolymer (in the ethylene interpolymer product) was replaced with a comparative ethylene interpolymer, where the first ethylene interpolymer was produced with a bridged metallocene catalyst formulation and the comparative ethylene interpolymer was produced with an unbridged single site catalyst formulation. Film examples also had improved machine direction 2% secant modulus (by at least 25%) and an improved transverse direction 2% secant modulus (by at least 50%); relative to a film produced from the comparative ethylene interpolymer. Further film embodiments had an improved machine direction tensile yield (by at least 10%) and an improved transverse direction tensile yield (by at least 30%); relative to the film produced from the comparative ethylene interpolymer. Films disclosed herein had improved (lower) hexane extractables, i.e. the amount of hexane soluble material (weight %) extracted from films containing the ethylene interpolymer product was about 50% lower, relative to films prepared from the comparative ethylene interpolymer. Additional film embodiments had improved (lower) seal initiation temperature (at least 5% lower), relative to films prepared from comparative ethylene interpolymers. The hot tack performance of films prepared from the disclosed ethylene interpolymer products were also improved; e.g., the temperature at the onset of film Tack (at a force of 1.0N) was improved (lower by about 10%), relative to a comparative polyethylene film of the same composition but said first ethylene interpolymer (in the ethylene interpolymer product) was replaced with a comparative ethylene interpolymer; where the first ethylene interpolymer was produced with a bridged metallocene catalyst formulation and the comparative ethylene interpolymer was produced with an unbridged single site catalyst formulation. Films disclosed herein also had improved dart impact. For example, the dart impact of a film prepared from an ethylene interpolymer product was about 100% higher, relative to a film prepared from the comparative ethylene interpolymer.

Further embodiments include polyethylene films comprising at least one layer, where the layer comprises at least one ethylene interpolymer product and at least one second polymer. Non-limiting examples of second polymers include ethylene polymers, propylene polymers or a mixture of ethylene polymers and propylene polymers.

Additional embodiments include a polyethylene films having a thickness from about 0.5 mil to about 10 mil. Embodiments also include multilayer films comprises from 2 to 11 layers, where at least one layer comprises at least one of the ethylene interpolymer products disclosed herein.

BRIEF DESCRIPTION OF FIGURES

The following Figures are presented for the purpose of illustrating selected embodiments of this disclosure; it being understood, that the embodiments in this disclosure are not limited to the precise arrangement of, or the number of, vessels shown.

FIG. 1 shows the determination of the Long Chain Branching Factor (LCBF). The abscissa plotted was the log of the corrected Zero Shear Viscosity (log(ZSV_(c))) and the ordinate plotted was the log of the corrected Intrinsic Viscosity (log(IV_(c))). Ethylene polymers that do not have LCB, or undetectable LCB, fall on the reference line. Ethylene polymers having LCB deviate from the reference line and were characterized by the dimensionless Long Chain Branching Factor (LCBF). LCBF=(S_(h)×S_(v))/2; where S_(h) and S_(v) are horizontal and vertical shift factors, respectively.

FIG. 2 illustrates a continuous solution polymerization process where a first homogeneous catalyst formulation and a second homogeneous catalyst formulation were employed in reactors 11 a and 12 a, respectively. Optionally (dotted lines) an in-line Ziegler-Natta catalyst formulation or a batch Ziegler-Natta catalyst formulation was employed in reactor 17.

FIG. 3 illustrates the nomenclature used to identify various carbon atoms that give rise to signals in ¹³C NMR spectra.

FIG. 4 deconvolution of ethylene interpolymer product Example 51 into a first, second and third ethylene interpolymer.

DEFINITION OF TERMS

Other than in the examples or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, extrusion conditions, etc., used in the specification and claims are to be understood as modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the desired properties that the various embodiments desire to obtain. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. The numerical values set forth in the specific examples are reported as precisely as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

It should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10; that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. Because the disclosed numerical ranges are continuous, they include every value between the minimum and maximum values. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations.

All compositional ranges expressed herein are limited in total to and do not exceed 100 percent (volume percent or weight percent) in practice. Where multiple components can be present in a composition, the sum of the maximum amounts of each component can exceed 100 percent, with the understanding that, and as those skilled in the art readily understand, that the amounts of the components actually used will conform to the maximum of 100 percent.

In order to form a more complete understanding of this disclosure the following terms are defined and should be used with the accompanying figures and the description of the various embodiments throughout.

As used herein, the term “monomer” refers to a small molecule that may chemically react and become chemically bonded with itself or other monomers to form a polymer.

As used herein, the term “α-olefin” is used to describe a monomer having a linear hydrocarbon chain containing from 3 to 20 carbon atoms having a double bond at one end of the chain; an equivalent term is “linear α-olefin”.

As used herein, the term “ethylene polymer”, refers to macromolecules produced from ethylene monomers and optionally one or more additional monomers; regardless of the specific catalyst or specific process used to make the ethylene polymer. In the polyethylene art, the one or more additional monomers are called “comonomer(s)” and often include α-olefins. The term “homopolymer” refers to a polymer that contains only one type of monomer. Common ethylene polymers include high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultralow density polyethylene (ULDPE), plastomer and elastomers. The term ethylene polymer also includes polymers produced in a high pressure polymerization processes; non-limiting examples include low density polyethylene (LDPE), ethylene vinyl acetate copolymers (EVA), ethylene alkyl acrylate copolymers, ethylene acrylic acid copolymers and metal salts of ethylene acrylic acid (commonly referred to as ionomers). The term ethylene polymer also includes block copolymers which may include 2 to 4 comonomers. The term ethylene polymer also includes combinations of, or blends of, the ethylene polymers described above.

The term “ethylene interpolymer” refers to a subset of polymers within the “ethylene polymer” group that excludes polymers produced in high pressure polymerization processes; non-limiting examples of polymer produced in high pressure processes include LDPE and EVA (the latter is a copolymer of ethylene and vinyl acetate).

The term “heterogeneous ethylene interpolymers” refers to a subset of polymers in the ethylene interpolymer group that are produced using a heterogeneous catalyst formulation; non-limiting examples of which include Ziegler-Natta or chromium catalysts.

The term “homogeneous ethylene interpolymer” refers to a subset of polymers in the ethylene interpolymer group that are produced using homogeneous catalyst formulations. Typically, homogeneous ethylene interpolymers have narrow molecular weight distributions, for example Size Exclusion Chromatography (SEC) M_(w)/M_(n) values of less than 2.8; M_(w) and M_(n) refer to weight and number average molecular weights, respectively. In contrast, the M_(w)/M_(n) of heterogeneous ethylene interpolymers are typically greater than the M_(w)/M_(n) of homogeneous ethylene interpolymers. In general, homogeneous ethylene interpolymers also have a narrow comonomer distribution, i.e. each macromolecule within the molecular weight distribution has a similar comonomer content. Frequently, the composition distribution breadth index “CDBI” is used to quantify how the comonomer is distributed within an ethylene interpolymer, as well as to differentiate ethylene interpolymers produced with different catalysts or processes. The “CDBI₅₀” is defined as the percent of ethylene interpolymer whose composition is within 50% of the median comonomer composition; this definition is consistent with that described in U.S. Pat. No. 5,206,075 assigned to Exxon Chemical Patents Inc. The CDBI₅₀ of an ethylene interpolymer can be calculated from TREF curves (Temperature Rising Elution Fractionation); the TREF method is described in Wild, et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455. Typically the CDBI₅₀ of homogeneous ethylene interpolymers are greater than about 70%. In contrast, the CDBI₅₀ of α-olefin containing heterogeneous ethylene interpolymers are generally lower than the CDBI₅₀ of homogeneous ethylene interpolymers. A blend of two or more homogeneous ethylene interpolymers, that differ in comonomer content, may have a CDBI₅₀ less than 70%; in this disclosure such a blend was defined as a homogeneous blend or homogeneous composition. Similarly, a blend of two or more homogeneous ethylene interpolymers, that differ in weight average molecular weight (M_(w)), may have a M_(w)/M_(n)≥2.8; in this disclosure such a blend was defined as a homogeneous blend or homogeneous composition.

In this disclosure, the term “homogeneous ethylene interpolymer” refers to both linear homogeneous ethylene interpolymers and substantially linear homogeneous ethylene interpolymers. In the art, linear homogeneous ethylene interpolymers are generally assumed to have no long chain branches or an undetectable amount of long chain branches; while substantially linear ethylene interpolymers are generally assumed to have greater than about 0.01 to about 3.0 long chain branches per 1000 carbon atoms. A long chain branch is macromolecular in nature, i.e. similar in length to the macromolecule that the long chain branch is attached to.

In this disclosure the term homogeneous catalyst is used, for example to describe a first, a second, a third, a fourth and a fifth homogeneous catalyst formulation. The term catalyst refers to the chemical compound containing the catalytic metal, which is a metal-ligand complex. In this disclosure, the term ‘homogeneous catalyst’ is defined by the characteristics of the polymer produced by the homogeneous catalyst. Specifically, a catalyst is a homogeneous catalyst if it produces a homogeneous ethylene interpolymer that has a narrow molecular weight distribution (SEC M_(w)/M_(n) values of less than 2.8) and a narrow comonomer distribution (CDBI₅₀>70%). Homogeneous catalysts are well known in the art. Two subsets of the homogeneous catalyst genus include unbridged metallocene catalysts and bridged metallocene catalysts. Unbridged metallocene catalysts are characterized by two bulky ligands bonded to the catalytic metal, a non-limiting example includes bis(isopropyl-cyclopentadienyl) hafnium dichloride. In bridged metallocene catalysts the two bulky ligands are covalently bonded (bridged) together, a non-limiting example includes diphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfuorenyl) hafnium dichloride; wherein the diphenylmethylene group bonds, or bridges, the cyclopentadienyl and fluorenyl bulky ligands together. Two additional subsets of the homogeneous catalyst genus include unbridged and bridged single site catalysts. In this disclosure, single site catalysts are characterized as having only one bulky ligand bonded to the catalytic metal. A non-limiting example of an unbridged single site catalyst includes cyclopentadienyl tri(tertiary butyl)phosphinimine titanium dichloride. A non-limiting example of a bridged single site catalyst includes [C₅(CH₃)₄—Si(CH₃)₂—N(tBu)] titanium dichloride, where the —Si(CH₃)₂— group functions as the bridging group.

Herein, the term “polyolefin” includes ethylene polymers and propylene polymers; non-limiting examples of propylene polymers include isotactic, syndiotactic and atactic propylene homopolymers, random propylene copolymers containing at least one comonomer (e.g. α-olefins) and impact polypropylene copolymers or heterophasic polypropylene copolymers.

The term “thermoplastic” refers to a polymer that becomes liquid when heated, will flow under pressure and solidify when cooled. Thermoplastic polymers include ethylene polymers as well as other polymers used in the plastic industry; non-limiting examples of other polymers commonly used in film applications include barrier resins (EVOH), tie resins, polyethylene terephthalate (PET), polyamides and the like.

As used herein the term “monolayer film” refers to a film containing a single layer of one or more thermoplastics.

As used herein, the terms “hydrocarbyl”, “hydrocarbyl radical” or “hydrocarbyl group” refers to linear, branched, or cyclic, aliphatic, olefinic, acetylenic and aryl (aromatic) radicals comprising hydrogen and carbon that are deficient by one hydrogen.

As used herein, an “alkyl radical” includes linear, branched and cyclic paraffin radicals that are deficient by one hydrogen radical; non-limiting examples include methyl (—CH₃) and ethyl (—CH₂CH₃) radicals. The term “alkenyl radical” refers to linear, branched and cyclic hydrocarbons containing at least one carbon-carbon double bond that is deficient by one hydrogen radical.

As used herein, the term “aryl” group includes phenyl, naphthyl, pyridyl and other radicals whose molecules have an aromatic ring structure; non-limiting examples include naphthylene, phenanthrene and anthracene. An “arylalkyl” group is an alkyl group having an aryl group pendant there from; non-limiting examples include benzyl, phenethyl and tolylmethyl; an “alkylaryl” is an aryl group having one or more alkyl groups pendant there from; non-limiting examples include tolyl, xylyl, mesityl and cumyl.

As used herein, the phrase “heteroatom” includes any atom other than carbon and hydrogen that can be bound to carbon. A “heteroatom-containing group” is a hydrocarbon radical that contains a heteroatom and may contain one or more of the same or different heteroatoms. In one embodiment, a heteroatom-containing group is a hydrocarbyl group containing from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur. Non-limiting examples of heteroatom-containing groups include radicals of imines, amines, oxides, phosphines, ethers, ketones, oxoazolines heterocyclics, oxazolines, thioethers, and the like. The term “heterocyclic” refers to ring systems having a carbon backbone that comprise from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur.

As used herein the term “unsubstituted” means that hydrogen radicals are bounded to the molecular group that follows the term unsubstituted. The term “substituted” means that the group following this term possesses one or more moieties that have replaced one or more hydrogen radicals in any position within the group; non-limiting examples of moieties include halogen radicals (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, C₁ to C₁₀ alkyl groups, C₂ to C₁₀ alkenyl groups, and combinations thereof. Non-limiting examples of substituted alkyls and aryls include: acyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals and combinations thereof.

Herein the term “R1” and its superscript form “^(R1)” refers to a first reactor in a continuous solution polymerization process; it being understood that R1 is distinctly different from the symbol R¹; the latter is used in chemical formula, e.g. representing a hydrocarbyl group. Similarly, the term “R2” and it's superscript form “^(R2)” refers to a second reactor, and; the term “R3” and it's superscript form “^(R3)” refers to a third reactor.

As used herein, the term “oligomers” refers to an ethylene polymer of low molecular weight, e.g., an ethylene polymer with a weight average molecular weight (Mw) of about 2000 to 3000 daltons. Other commonly used terms for oligomers include “wax” or “grease”. As used herein, the term “light-end impurities” refers to chemical compounds with relatively low boiling points that may be present in the various vessels and process streams within a continuous solution polymerization process; non-limiting examples include, methane, ethane, propane, butane, nitrogen, CO₂, chloroethane, HCl, etc.

DETAILED DESCRIPTION

Catalysts

Catalyst formulations that are efficient in polymerizing olefins are well known. In the embodiments disclosed herein, at least two catalyst formulations were employed in a continuous solution polymerization process. One of the catalyst formulations comprised a first homogeneous catalyst formulation that produces a homogeneous first ethylene interpolymer in a first reactor, one embodiment of the first homogeneous catalyst formulation was a bridged metallocene catalyst formulation (Formula (I)). The other catalyst formulation comprised a second homogeneous catalyst formulation that produced a second ethylene interpolymer in a second reactor, one embodiment of the second homogeneous catalyst formulation was an unbridged single site catalyst formulation (Formula (II)). Optionally a third ethylene interpolymer may be produced in a third reactor using one or more of: the first, the second, a third homogeneous catalyst formulation, a fifth homogeneous catalyst formulation or a heterogeneous catalyst formulation. One embodiment of the third homogeneous catalyst formulation was an unbridged single site catalyst formulation (Formula (II)). The fifth homogeneous catalyst formulation was selected from the first, the second, the third and/or a fourth homogeneous catalyst formulation; where the fourth homogeneous catalyst formulation contains a bulky ligand-metal complex that was not a species of the chemical genera defined by Formula (I) or Formula (II). In the continuous solution process disclosed, at least two homogeneous ethylene interpolymers were produced and solution blended to produce an ethylene interpolymer product.

Bulky Ligand-Metal Complexes

Component A

The present disclosure included “a first homogeneous catalyst formulation”. One embodiment of the first homogeneous catalyst formulation was “a bridged metallocene catalyst formulation” containing a bulky ligand-metal complex, hereinafter “component A”, represented by Formula (I).

In Formula (I): non-limiting examples of M include Group 4 metals, i.e. titanium, zirconium and hafnium; non-limiting examples of G include Group 14 elements, carbon, silicon, germanium, tin and lead; X represents a halogen atom, fluorine, chlorine, bromine or iodine; the R₆ groups are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical (these radicals may be linear, branched or cyclic or further substituted with halogen atoms, C₁₋₁₀ alkyl radicals, C₁₋₁₀ alkoxy radicals, C₆₋₁₀ aryl or aryloxy radicals); R₁ represents a hydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R₂ and R₃ are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical, and; R₄ and R₅ are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical.

In the art, a commonly used term for the X(R₆) group shown in Formula (I) is “leaving group”, i.e. any ligand that can be abstracted from Formula (I) forming a catalyst species capable of polymerizing one or more olefin(s). An equivalent term for the X(R₆) group is an “activatable ligand”. Further non-limiting examples of the X(R₆) group shown in Formula (I) include weak bases such as amines, phosphines, ethers, carboxylates and dienes. In another embodiment, the two R₆ groups may form part of a fused ring or ring system.

Further embodiments of component A include structural, optical or enantiomeric isomers (meso and racemic isomers) and mixtures thereof of the structure shown in Formula (I).

In this disclosure, various species of component A (Formula (I)) were denoted by the terms “component A1”, “component A2” and “component A3”, etc. While not to be construed as limiting, two species of component A were employed as examples in this disclosure. Specifically: “component A1” refers to diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafnium dichloride having the molecular formula [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂], and; “component A2” refers to diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafnium dimethyl having the molecular formula [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂]. In this disclosure, component A1 and component A2 were used to prepare examples of the bridged metallocene catalyst formulation.

Long Chain Branching in Ethylene Interpolymer Products (Via Component A)

In this disclosure, the first homogeneous catalyst formulation, comprising a component A, produces ethylene interpolymer products that have long chain branches, hereinafter ‘LCB’.

LCB is a well-known structural phenomenon in polyethylenes and well known to those of ordinary skill in the art. Traditionally, there are three methods for LCB analysis, namely, nuclear magnetic resonance spectroscopy (NMR), for example see J. C. Randall, J Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, 29, 201; triple detection SEC equipped with a DRI, a viscometer and a low-angle laser light scattering detector, for example see W. W. Yau and D. R. Hill, Int. J. Polym. Anal. Charact. 1996; 2:151; and rheology, for example see W. W. Graessley, Acc. Chem. Res. 1977, 10, 332-339. In this disclosure, a long chain branch is macromolecular in nature, i.e. long enough to be seen in an NMR spectra, triple detector SEC experiments or rheological experiments.

A limitation with LCB analysis via NMR is that it cannot distinguish branch length for branches equal to or longer than six carbon atoms (thus, NMR cannot be used to characterize LCB in ethylene/1-octene copolymers, which have hexyl groups as side branches).

The triple detection SEC method measures the intrinsic viscosity ([η]) (see W. W. Yau, D. Gillespie, Analytical and Polymer Science, TAPPI Polymers, Laminations, and Coatings Conference Proceedings, Chicago 2000; 2: 699 or F. Beer, G. Capaccio, L. J. Rose, J. Appl. Polym. Sci. 1999, 73: 2807 or P. M. Wood-Adams, J. M. Dealy, A. W. deGroot, O. D. Redwine, Macromolecules 2000; 33: 7489). By referencing the intrinsic viscosity of a branched polymer ([η]_(b)) to that of a linear one ([θ]_(l)) at the same molecular weight, the viscosity branching index factor g′ (g′=[η]_(b)/[η]_(l)) was used for branching characterization. However, both short chain branching (SCB) and long chain branching (LCB) make contribution to the intrinsic viscosity ([η]), effort was made to isolate the SCB contribution for ethylene/1-butene and ethylene/1-hexene copolymers but not ethylene/1-octene copolymers (see Lue et al., U.S. Pat. No. 6,870,010 B1). In this disclosure, a systematical investigation was performed to look at the SCB impact on the Mark-Houwink constant K for three types ethylene/1-olefin copolymers, i.e. octene, hexene and butene copolymers. After the deduction of SCB contribution, a Viscosity LCB Index was introduced for the characterization of ethylene/1-olefin copolymers containing LCB. The Viscosity LCB Index was defined as the measured Mark-Houwink constant (K_(m)) in 1,2,4-trichlorobenzene (TCB) at 140° C. for the sample divided by the SCB corrected Mark-Houwink constant (K_(co)) for linear ethylene/1-olefin copolymer, Eq.(1).

$\begin{matrix} {{{Viscosity}\mspace{14mu}{LCB}\mspace{14mu}{Index}} = {\frac{K_{m}}{K_{co}} = \frac{\lbrack\eta\rbrack/M_{v}^{0.725}}{\left( {391.98 - {A \times {SCB}}} \right)/1000000}}} & {{Eq}.\mspace{14mu}(1)} \end{matrix}$ Where [η] was the intrinsic viscosity (dL/g) determined by 3D-SEC, M_(v) was the viscosity average molar mass (g/mole) determined using 3D-SEC; SCB was the short chain branching content (CH₃#/1000C) determined using FTIR, and; A was a constant which depends on the α-olefin present in the ethylene/α-olefin interpolymer under test, specifically, A is 2.1626, 1.9772 and 1.1398 for 1-octene, 1-hexene and 1-butene respectively. In the case of an ethylene homopolymer no correction is required for the Mark-Houwink constant, i.e. SCB is zero.

In the art, rheology has also been an effective method to measure the amount of LCB, or lack of, in ethylene interpolymers. Several rheological methods to quantify LCB have been disclosed. One commonly-used method was based on zero-shear viscosity (η₀) and weight average molar mass (M_(w)) data. The 3.41 power dependence (η₀=K×M_(w) ^(3.41)) has been established for monodisperse polyethylene solely composed of linear chains, for example see R. L. Arnett and C. P. Thomas, J. Phys. Chem. 1980, 84, 649-652. An ethylene polymer with a η₀ exceeding what was expected for a linear ethylene polymer, with the same M_(w), was considered to contain long-chain branches. However, there is a debate in the field regarding the influence of polydispersity, e.g. M_(w)/M_(n). A dependence on polydispersity was observed in some cases (see M. Ansari et al., Rheol. Acta, 2011, 5017-27) but not in others (see T. P. Karjala et al., Journal of Applied Polymer Science 2011, 636-646).

Another example of LCB analysis via rheology was based on zero-shear viscosity (η₀) and intrinsic viscosity ([η]) data, for example see R. N. Shroff and H. Mavridis, Macromolecules 1999, 32, 8454; which is applicable for essentially linear polyethylenes (i.e. polyethylenes with very low levels of LCB). A critical limitation of this method is the contribution of the SCB to the intrinsic viscosity. It is well known that [η] decreases with increasing SCB content.

In this disclosure, a systematical investigation was performed to look at the impact of both SCB and molar mass distribution. After the deduction of the contribution of both SCB and molar mass distribution (polydispersity), a Long Chain Branching Factor (LCBF) was introduced to characterize the amount of LCB in ethylene/α-olefin copolymers, as described below.

Long Chain Branching Factor (LCBF)

In this disclosure the Long Chain Branching Factor, hereinafter LCBF, was used to characterize the amount of LCB in ethylene interpolymer products. The disclosed ethylene interpolymer products were in-situ blends of at least two ethylene interpolymers produced with at least two different catalyst formulations.

FIG. 1 illustrates the calculation of the LCBF. The solid ‘Reference Line’ shown in FIG. 1 characterizes ethylene polymers that do not contain LCB (or undetectable LCB). Ethylene polymers containing LCB deviate from this Reference Line. For example, the disclosed ethylene interpolymer products Examples 50-52 (the ‘+’ symbols FIG. 1) deviate horizontally and vertically from the Reference Line.

LCBF calculation requires the polydispersity corrected Zero Shear Viscosity (ZSV_(c)) and the SCB corrected Intrinsic Viscosity (IV_(c)) as fully described in the following paragraphs.

The correction to the Zero Shear Viscosity, ZSV_(c), having dimensions of poise, was performed as shown in equation Eq.(2):

$\begin{matrix} {{ZSV}_{c} = \frac{1.8389 \times \eta_{0}}{2.4110^{{Ln}{({Pd})}}}} & {{Eq}.\mspace{14mu}(2)} \end{matrix}$ where η₀, the zero shear viscosity (poise), was measured by DMA as described in the ‘Testing Methods’ section of this disclosure; Pd was the dimensionless polydispersity (M_(w)/M_(n)) as measured using conventional SEC (see ‘Testing Methods’) and 1.8389 and 2.4110 are dimensionless constants.

The correction to the Intrinsic Viscosity, IV_(c), having dimensions of dL/g, was performed as shown in equation Eq.(3):

$\begin{matrix} {{IV}_{c} = {\lbrack\eta\rbrack + \frac{A \times {SCB} \times M_{v}^{0.725}}{1000000}}} & {{Eq}.\mspace{14mu}(3)} \end{matrix}$ where the intrinsic viscosity [η] (dL/g) was measured using 3D-SEC (see ‘Testing Methods’); SCB having dimensions of (CH₃#/1000C) was determined using FTIR (see ‘Testing Methods’); M_(v), the viscosity average molar mass (g/mole), was determined using 3D-SEC (see ‘Testing Methods’), and; A was a dimensionless constant that depends on the α-olefin in the ethylene/α-olefin interpolymer sample, i.e. A was 2.1626, 1.9772 or 1.1398 for 1-octene, 1-hexene and 1-butene α-olefins, respectively. In the case of an ethylene homopolymer no correction is required for the Mark-Houwink constant, i.e. SCB is zero.

As shown in FIG. 1, linear ethylene/α-olefin interpolymers (which do not contain LCB or contain undetectable levels of LCB) fall on the Reference Line defined by Eq.(4). Log(IV _(c))=0.2100×Log(ZSV _(c))−0.7879  Eq.(4)

Table 1A shows the Reference Resins had M_(w)/M_(n) values that ranged from 1.68 to 9.23 and contained 1-octene, 1-hexene or 1-butene α-olefins. Further, Reference Resins included ethylene polymers produced in solution, gas phase or slurry processes with Ziegler-Natta, homogeneous and mixed (Ziegler-Natta+homogeneous) catalyst formulations.

The ethylene interpolymer products, disclosed herein, contain long chain branching as evidenced by Table 2 and FIG. 1. More specifically, Table 2 discloses that the LCBF of Examples 50 through 52 and Example 58 were 0.00845, 0.0369, 0.0484 and 0.0417, respectively. Example 50-52 (+ symbol) and Example 58 (open square) deviate significantly from the Reference Line shown in FIG. 1. Examples 50 through 52 and Example 58 were produced using a bridged metallocene catalyst formulation in the first reactor and an unbridged single site catalyst formulation in the second reactor. In contrast, as shown in Table 2, Comparatives 61, 67 had much lower LCBF of 0.000330 and 0.000400, respectively, and these samples were well described by the linear Reference Line shown in FIG. 1 (the open triangle symbols), i.e. Comparatives 61 and 67 have not have LCB, or have an undetectable level of LCB.

Comparative 61 was produced in a solution process pilot plant using an unbridged single site catalyst formulation (Formula (II)) in both the first and second reactor, where the reactors were configured in series. Comparative 67 was produced in a commercial-scale solution process using an unbridged single site catalyst formulation in both the first and second reactor, where the reactors were configured in series.

As shown in FIG. 1, the calculation of the LCBF was based on the Horizontal-Shift (S_(h)) and Vertical-Shift (S_(v)) from the linear reference line, as defined by the following equations: S _(h)=Log(ZSV _(c))−4.7619×Log(IV _(c))−3.7519  Eq.(5) S _(v)=0.2100×Log(ZSV _(c))−Log(IV _(c))−0.7879  Eq.(6).

In Eq. (5) and (6), it is required that ZSV_(c) and IV_(c) have dimensions of poise and dL/g, respectively. The Horizontal-Shift (S_(h)) was a shift in ZSV_(c) at constant Intrinsic Viscosity (IV_(c)), if one removes the Log function its physical meaning is apparent, i.e. a ratio of two Zero Shear Viscosities, the ZSV_(c) of the sample under test relative to the ZSV_(c) of a linear ethylene polymer having the same IV_(c). The Horizontal-Shift (S_(h)) was dimensionless. The Vertical-Shift (S_(v)) was a shift in IV_(c) at constant Zero Shear Viscosity (ZSV_(c)), if one removes the Log function its physical meaning is apparent, i.e. a ratio of two Intrinsic Viscosities, the IV_(c) of a linear ethylene polymer having the same ZSV_(c) relative to the IV_(c) of the sample under test. The Vertical-Shift (S_(v)) was dimensionless.

The dimensionless Long Chain Branching Factor (LCBF) was defined by Eq.(7):

$\begin{matrix} {{LCBF} = \frac{S_{h} \times S_{v}}{2}} & {{Eq}.\mspace{14mu}(7)} \end{matrix}$

Given the data in Table 2, the LCBF of Examples and Comparatives were calculated. To be more clear, as shown in Table 2, the S_(h) and S_(v) of Example 51 were 0.593 and 0.124, respectively, thus the LCBF was 0.0368 ((0.593×0.124)/2). In contrast, the S_(h) and S_(v) of Comparative 61 were 0.0560 and 0.0118, respectively, thus the LCBF was 0.00033 ((0.0560×0.0118)/2).

In this disclosure, resins having no LCB (or undetectable LCB) were characterized by a LCBF of less than 0.001 (dimensionless), as evidenced by Table 1B where the reference resins had LCBF values ranging from 0.000426 to 1.47×10⁻⁹.

In this disclosure, resins having LCB were characterized by a LCBF of ≥0.001 (dimensionless), as evidenced by Examples 50-52 and Example 58 shown in Table 2 that had LCBF that ranged from 0.00845 and 0.0484.

Table 3 summarizes the LCBF of Comparatives A-C and Comparatives D-G. Comparatives A-C (open diamond in FIG. 1) were believed to be produced in a solution process employing one reactor and a constrained geometry single site catalyst formulation, i.e. AFFINITY™ PL 1880 (three different samples (lots)). AFFINITY™ products are ethylene/1-octene interpolymers available from The Dow Chemical Company (Midland, Mich., USA). It has been well documented in the art that the constrained geometry catalyst produces long chain branched ethylene/1-octene copolymers, as evidenced by the LCBF values disclosed in Table 3, i.e. from 0.0396 to 0.0423. Comparatives D-G (the open circles in FIG. 1) were believed to be solution process series dual reactor and dual catalyst ethylene interpolymers, where a constrained geometry single site catalyst formulation was employed in a first reactor and a batch Ziegler-Natta catalyst formulation was employed in a second reactor, i.e. Elite® 5401G and Elite® 5100G (two different samples (lots)) and Elite® 5400G, respectively. Elite® products are ethylene/1-octene interpolymers available from The Dow Chemical Company (Midland, Mich., USA). As shown in Table 3, Comparatives D-G had LCBF values from 0.00803 to 0.0130.

¹³C NMR Determination of Long Chain Branching in the First Ethylene Interpolymer

Examples of ethylene interpolymer product, disclosed herein, contain a first ethylene interpolymer that was produced with a first homogeneous catalyst formulation. One embodiment of the first homogenous catalyst formulation was a bridged metallocene catalyst formulation, this catalyst formulation produced a long chain branched (LCB) first ethylene interpolymer. Pure samples of the first ethylene interpolymer were produced using the Continuous Polymerization Unit (CPU). The CPU was fully described in the ‘Continuous Polymerization Unit (CPU)’ section of this disclosure. The CPU employs one reactor and one catalyst formulation was used. The CPU and the bridged metallocene catalyst formulation containing Component A [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂] were used to produce examples of the first ethylene interpolymer and the amount of long chain branching in this interpolymer was measured by ¹³C NMR. Table 13x illustrates typical CPU operating continues for the bridged metallocene catalyst formulating to produce a first ethylene interpolymer at three reactor temperatures (130° C., 160° C. and 190° C.) and two levels of ethylene conversion, i.e. low ethylene conversion (about 75%) and high ethylene conversion (about 94%). No hydrogen was used.

Table 14 discloses the amount of LCB in Examples C10 to C15, i.e. pure samples of the first ethylene interpolymer, produced with the bridged metallocene catalyst formulation, as determined by ¹³C-NMR (nuclear magnetic resonance). Examples C10 to C15 were ethylene homopolymers produced on the CPU at three reactor temperatures (190° C., 160° C. and 130° C.), three levels of ethylene conversions, i.e. about 95 wt %, about 85 wt % and about 75 wt % and no hydrogen was used. As shown in Table 14, the amount of long chain branching in the first ethylene interpolymer varied from 0.03 LCB/1000C to 0.23 LCB/1000C.

Component C

In this disclosure, at least two catalyst formulations were employed to synthesize embodiments of the ethylene interpolymer products. One catalyst formulation was the first homogeneous catalyst formulation; one embodiment of the first homogeneous catalyst was a bridged metallocene catalyst formulation containing component A, described above. The other catalyst formulation was the second homogeneous catalyst formulation; one embodiment of the second homogeneous catalyst formulation was “an unbridged single site catalyst formulation” containing a bulky ligand-metal complex, hereinafter “component C”, represented by Formula (II). (L ^(A))_(a) M(PI)_(b)(Q)_(n)  (II)

In Formula (II): (L^(A)) represents a bulky ligand; M represents a metal atom; PI represents a phosphinimine ligand; Q represents a leaving group; a is 0 or 1; b is 1 or 2; (a+b)=2; n is 1 or 2, and; the sum of (a+b+n) equals the valance of the metal M. Non-limiting examples of M in Formula (II) include Group 4 metals, titanium, zirconium and hafnium.

Non-limiting examples of the bulky ligand L^(A) in Formula (II) include unsubstituted or substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom substituted and/or heteroatom containing cyclopentadienyl-type ligands. Additional non-limiting examples include, cyclopentaphenanthreneyl ligands, unsubstituted or substituted indenyl ligands, benzindenyl ligands, unsubstituted or substituted fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, phosphinimine, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and the like, including hydrogenated versions thereof, for example tetrahydroindenyl ligands. In other embodiments, L^(A) may be any other ligand structure capable of q-bonding to the metal M, such embodiments include both η³-bonding and η⁵-bonding to the metal M. In other embodiments, L^(A) may comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur and phosphorous, in combination with carbon atoms to form an open, acyclic, or a fused ring, or ring system, for example, a heterocyclopentadienyl ancillary ligand. Other non-limiting embodiments for L^(A) include bulky amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines, corrins and other polyazomacrocycles.

The phosphinimine ligand, PI, is defined by Formula (III): (R^(p))₃ P═N—  (III) wherein the R^(p) groups are independently selected from: a hydrogen atom; a halogen atom; C₁₋₂₀ hydrocarbyl radicals which are unsubstituted or substituted with one or more halogen atom(s); a C₁₋₈ alkoxy radical; a C₆₋₁₀ aryl radical; a C₆₋₁₀ aryloxy radical; an amido radical; a silyl radical of formula —Si(R^(s))₃, wherein the R^(s) groups are independently selected from, a hydrogen atom, a C₁₋₈ alkyl or alkoxy radical, a C₆₋₁₀ aryl radical, a C₆₋₁₀ aryloxy radical, or a germanyl radical of formula —Ge(R^(G))₃, wherein the R^(G) groups are defined as R^(s) is defined in this paragraph.

The leaving group Q is any ligand that can be abstracted from Formula (II) forming a catalyst species capable of polymerizing one or more olefin(s). In some embodiments, Q is a monoanionic labile ligand having a sigma bond to M. Depending on the oxidation state of the metal, the value for n is 1 or 2 such that Formula (II) represents a neutral bulky ligand-metal complex. Non-limiting examples of Q ligands include a hydrogen atom, halogens, C₁₋₂₀ hydrocarbyl radicals, C₁₋₂₀ alkoxy radicals, C₅₋₁₀ aryl oxide radicals; these radicals may be linear, branched or cyclic or further substituted by halogen atoms, C₁₋₁₀ alkyl radicals, C₁₋₁₀ alkoxy radicals, C₆₋₁₀ arly or aryloxy radicals. Further non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms. In another embodiment, two Q ligands may form part of a fused ring or ring system.

Further embodiments of component C include structural, optical or enantiomeric isomers (meso and racemic isomers) and mixtures thereof of the bulky ligand-metal complex shown in Formula (II).

In this disclosure, unique chemical species of component C (Formula (II)) are denoted by the terms “component C1”, “component C2” and “component C3”, etc. While not to be construed as limiting, two species of component C were employed as examples in this disclosure. Specifically: “component C1” refers to cyclopentadienyl tri(tertiary butyl) phosphinimine titanium dichloride having the molecular formula [Cp[(t-Bu)₃PN]TiCl₂] abbreviated “PIC-1” in Table 4A, and; “component C2” refers to cyclopentadienyl tri(isopropyl)phosphinimine titanium dichloride having the molecular formula [Cp[(isopropyl)₃PN]TiCl₂] abbreviated “PIC-2” in Table 4A. In this disclosure, component C1 and component C2 were used as the source of bulky ligand-metal complex to prepare two examples of the unbridged single site catalyst formulation.

Comparative Ethylene Interpolymer Products

In this disclosure, Comparative ethylene interpolymer products were produced by replacing the first homogeneous catalyst formulation, responsible for producing the first ethylene interpolymer, with a third homogeneous catalyst formulation. One embodiment of the third homogeneous catalyst formulation was an unbridged single site catalyst formulation where the bulky ligand-metal complex was a member of the genus defined by Formula (II), for example component C described above. As shown in Table 4A, Comparative 60 was produced employing PIC-2 in both reactors 1 and 2, where reactor 1 and 2 were configured in series. Comparative 61 was produced employing PIC-1 in both reactors 1 and 2, where reactor 1 and 2 were configured in parallel. Comparative 67 was produced employing an unbridged single site catalyst formulation in both reactors 1 and 2, where reactor 1 and 2 were configured in parallel. As shown in Table 2 and FIG. 1, Comparatives 61 and 67 had undetectable levels of LCB, as evidenced by the dimensionless Long Chain Branching Factor (LCBF) of less than 0.001, e.g. LCBF ranged from 0.00033 to 0.00040, respectively.

Homogeneous Catalyst Formulations

In this disclosure the non-limiting “Examples” of ethylene interpolymer product were prepared by employing a bridged metallocene catalyst formulation in a first reactor. The bridged metallocene catalyst formulation contains a component A (defined above), a component M^(A), a component B^(A) and a component P^(A). Components M, B and P are defined below and the superscript “^(A)” denotes that fact that the respective component was part of the catalyst formulation containing component A, i.e. the bridged metallocene catalyst formulation.

In this disclosure “Comparative” ethylene interpolymers were prepared by employing an unbridged single site catalyst formulation in the first reactor. In other words, in Comparative samples, the unbridged single site catalyst formulation replaced the bridged metallocene catalyst formulation in the first reactor. The unbridged single site catalyst formulation contains a component C (defined above), a component M^(C), a component B^(C) and a component P^(C). Components M, B and P are defined below and the superscript “^(C)” denoted that fact that the respective component was part of the catalyst formulation containing component C, i.e. the unbridged single site catalyst formulation.

The catalyst components M, B and P were independently selected for each catalyst formulation. To be more clear: components M^(A) and M^(C) may, or may not be, the same chemical compound; components B^(A) and B^(C) may, or may not be, the same chemical compound, and; components P^(A) and P^(C) may, or may not be, the same chemical compound. Further, catalyst activity was optimized by independently adjusting the mole ratios of the components in each catalyst formulation.

Components M, B and P were not particularly limited, i.e. a wide variety of components can be used as described below.

Component M functioned as a co-catalyst that activated component A or component C, into a cationic complex that effectively polymerized ethylene, or mixtures of ethylene and α-olefins, producing high molecular weight ethylene interpolymers. In the bridged metallocene catalyst formulation and the unbridged single site catalyst formulation the respective component M was independently selected from a variety of compounds and those skilled in the art will understand that the embodiments in this disclosure are not limited to the specific chemical compound disclosed. Suitable compounds for component M included an alumoxane co-catalyst (an equivalent term for alumoxane is aluminoxane). Although the exact structure of an alumoxane co-catalyst was uncertain, subject matter experts generally agree that it was an oligomeric species that contain repeating units of the general Formula (IV): (R)₂AlO—(Al(R)—O)_(n)—Al(R)₂  (IV) where the R groups may be the same or different linear, branched or cyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n is from 0 to about 50. A non-limiting example of an alumoxane was methyl aluminoxane (or MMAO-7) wherein each R group in Formula (IV) is a methyl radical.

Component B was an ionic activator. In general, ionic activators are comprised of a cation and a bulky anion; wherein the latter is substantially non-coordinating. In the bridged metallocene catalyst formulation and the unbridged single site catalyst formulation the respective component B was independently selected from a variety of compounds and those skilled in the art will understand that the embodiments in this disclosure are not limited to the specific chemical compound disclosed. Non-limiting examples of component B were boron ionic activators that are four coordinate with four ligands bonded to the boron atom. Non-limiting examples of boron ionic activators included the following Formulas (V) and (VI) shown below; [R⁵]⁺[B(R⁷)₄]⁻  (V) where B represented a boron atom, R⁵ was an aromatic hydrocarbyl (e.g. triphenyl methyl cation) and each R⁷ was independently selected from phenyl radicals which were unsubstituted or substituted with from 3 to 5 substituents selected from fluorine atoms, C₁₋₄ alkyl or alkoxy radicals which were unsubstituted or substituted by fluorine atoms; and a silyl radical of formula —Si(R⁹)₃, where each R⁹ was independently selected from hydrogen atoms and C₁₋₄ alkyl radicals, and; compounds of formula (VI); [(R⁸)_(t)ZH]⁺[B(R⁷)₄]⁻  (VI) where B was a boron atom, H was a hydrogen atom, Z was a nitrogen or phosphorus atom, t was 2 or 3 and R⁸ was selected from C₁₋₈ alkyl radicals, phenyl radicals which were unsubstituted or substituted by up to three C₁₋₄ alkyl radicals, or one R⁸ taken together with the nitrogen atom may form an anilinium radical and R⁷ was as defined above in Formula (VI).

In both Formula (V) and (VI), a non-limiting example of R⁷ was a pentafluorophenyl radical. In general, boron ionic activators may be described as salts of tetra(perfluorophenyl) boron; non-limiting examples include anilinium, carbonium, oxonium, phosphonium and sulfonium salts of tetra(perfluorophenyl)boron with anilinium and trityl (or triphenylmethylium). Additional non-limiting examples of ionic activators included: triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron, N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron, di-(isopropyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropillium tetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate, benzene(diazonium)tetrakispentafluorophenyl borate, tropillium tetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium) tetrakis(3,4,5-trifluorophenyl)borate, tropillium tetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium) tetrakis(3,4,5-trifluorophenyl)borate, tropillium tetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethylium tetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium) tetrakis(1,2,2-trifluoroethenyl)borate, tropillium tetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium) tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily available commercial ionic activators included N,N-dimethylanilinium tetrakispentafluorophenyl borate, and triphenylmethylium tetrakispentafluorophenyl borate.

Component P is a hindered phenol and is an optional component in the respective catalyst formulation. In the bridged metallocene catalyst formulation and the unbridged single site catalyst formulation the respective component P was independently selected from a variety of compounds and those skilled in the art will understand that the embodiments in this disclosure are not limited to the specific chemical compound disclosed. Non-limiting example of hindered phenols included butylated phenolic antioxidants, butylated hydroxytoluene, 2,4-di-tertiarybutyl-6-ethyl phenol, 4,4′-methylenebis (2,6-di-tertiary-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

As fully described below, a highly active first homogeneous catalyst formulation, or in one specific embodiment a highly active bridged metallocene catalyst formulation was produced by optimizing the quantity and mole ratios of the four components in the formulation; for example, component A1, component M^(A1), component B^(A1) and component P^(A1). Where highly active means a very large amount of ethylene interpolymer is produced from a very small amount of catalyst formulation. Similarly, a highly active third homogeneous catalyst formulation or an unbridged single site catalyst formulation (comparative catalyst formulations) were produced by optimizing the quantity and mole ratios of the four components in the formulation; e.g., one embodiment comprises a component C1, a component M^(C1), a component B^(C1) and a component P^(C1).

Heterogeneous Catalyst Formulations

A number of heterogeneous catalyst formulations are well known to those skilled in the art, including, as non-limiting examples, Ziegler-Natta and chromium catalyst formulations. In this disclosure, optionally a heterogeneous catalyst formulation may be employed to synthesize the third ethylene interpolymer in a third reactor. The catalytic metal in the heterogeneous catalyst formulation was identified by the term “metal Z”.

In this disclosure, embodiments were described where the heterogeneous catalyst formulation was “an in-line Ziegler-Natta catalyst formulation” or “a batch Ziegler-Natta catalyst formation”. The term “in-line” referred to the continuous synthesis of a small quantity of active Ziegler-Natta catalyst and immediately injecting this catalyst into the third reactor, wherein ethylene and one or more optional α-olefins were polymerized to form the optional third ethylene interpolymer. The term “batch” referred to the synthesis of a much larger quantity of catalyst or procatalyst in one or more mixing vessels that were external to, or isolated from, the continuously operating solution polymerization process. Once prepared, the batch Ziegler-Natta catalyst formulation, or batch Ziegler-Natta procatalyst, was transferred to a catalyst storage tank. The term “procatalyst” referred to an inactive catalyst formulation (inactive with respect to ethylene polymerization); the procatalyst was converted into an active catalyst by adding an alkyl aluminum co-catalyst. As needed, the procatalyst was pumped from the storage tank to at least one continuously operating reactor, wherein an active catalyst polymerizes ethylene and one or more optional α-olefins to form an ethylene interpolymer. The procatalyst may be converted into an active catalyst in the reactor or external to the reactor.

A wide variety of chemical compounds can be used to synthesize an active Ziegler-Natta catalyst formulation. The following describes various chemical compounds that may be combined to produce an active Ziegler-Natta catalyst formulation. Those skilled in the art will understand that the embodiments in this disclosure are not limited to the specific chemical compound disclosed.

An active Ziegler-Natta catalyst formulation may be formed from: a magnesium compound, a chloride compound, a metal compound, an alkyl aluminum co-catalyst and an aluminum alkyl. In this disclosure, the term “component (v)” is equivalent to the magnesium compound, the term “component (vi)” is equivalent to the chloride compound, the term “component (vii)” is equivalent to the metal compound, the term “component (viii)” is equivalent to the alkyl aluminum co-catalyst and the term “component (ix)” is equivalent to the aluminum alkyl. As will be appreciated by those skilled in the art, Ziegler-Natta catalyst formulations may contain additional components; a non-limiting example of an additional component is an electron donor, e.g. amines or ethers.

A non-limiting example of an active in-line Ziegler-Natta catalyst formulation can be prepared as follows. In the first step, a solution of a magnesium compound (component (v)) is reacted with a solution of the chloride compound (component (vi)) to form a magnesium chloride support suspended in solution. Non-limiting examples of magnesium compounds include Mg(R¹)₂; wherein the R¹ groups may be the same or different, linear, branched or cyclic hydrocarbyl radicals containing 1 to 10 carbon atoms. Non-limiting examples of chloride compounds include R²Cl; wherein R² represents a hydrogen atom, or a linear, branched or cyclic hydrocarbyl radical containing 1 to 10 carbon atoms. In the first step, the solution of magnesium compound may also contain an aluminum alkyl (component (ix)). Non-limiting examples of aluminum alkyl include Al(R³)₃, wherein the R³ groups may be the same or different, linear, branched or cyclic hydrocarbyl radicals containing from 1 to 10 carbon atoms. In the second step a solution of the metal compound (component (vii)) is added to the solution of magnesium chloride and the metal compound is supported on the magnesium chloride. Non-limiting examples of suitable metal compounds include M(X)_(n) or MO(X)_(n); where M represents a metal selected from Group 4 through Group 8 of the Periodic Table, or mixtures of metals selected from Group 4 through Group 8; O represents oxygen, and; X represents chloride or bromide; n is an integer from 3 to 6 that satisfies the oxidation state of the metal. Additional non-limiting examples of suitable metal compounds include Group 4 to Group 8 metal alkyls, metal alkoxides (which may be prepared by reacting a metal alkyl with an alcohol) and mixed-ligand metal compounds that contain a mixture of halide, alkyl and alkoxide ligands. In the third step a solution of an alkyl aluminum co-catalyst (component (viii)) is added to the metal compound supported on the magnesium chloride. A wide variety of alkyl aluminum co-catalysts are suitable, as expressed by Formula (VII): Al(R⁴)_(p)(OR⁵)_(q)(X)_(r)  (VII) wherein the R⁴ groups may be the same or different, hydrocarbyl groups having from 1 to 10 carbon atoms; the OR⁵ groups may be the same or different, alkoxy or aryloxy groups wherein R⁵ is a hydrocarbyl group having from 1 to 10 carbon atoms bonded to oxygen; X is chloride or bromide, and; (p+q+r)=3, with the proviso that p is greater than 0. Non-limiting examples of commonly used alkyl aluminum co-catalysts include trimethyl aluminum, triethyl aluminum, tributyl aluminum, dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminum butoxide, dimethyl aluminum chloride or bromide, diethyl aluminum chloride or bromide, dibutyl aluminum chloride or bromide and ethyl aluminum dichloride or dibromide.

The process described in the paragraph above, to synthesize an active in-line Ziegler-Natta catalyst formulation, can be carried out in a variety of solvents; non-limiting examples of solvents include linear or branched C₅ to C₁₂ alkanes or mixtures thereof.

To produce an active in-line Ziegler-Natta catalyst formulation the quantity and mole ratios of the five components, (v) through (ix), are optimized as described below.

Additional embodiments of heterogeneous catalyst formulations include formulations where the “metal compound” is a chromium compound; non-limiting examples include silyl chromate, chromium oxide and chromocene. In some embodiments, the chromium compound is supported on a metal oxide such as silica or alumina. Heterogeneous catalyst formulations containing chromium may also include co-catalysts; non-limiting examples of co-catalysts include trialkylaluminum, alkylaluminoxane and dialkoxyalkylaluminum compounds and the like.

Solution Polymerization Process

The disclosed continuous solution polymerization process is improved by having one or more of: 1) at least a 70% reduced [α-olefin/ethylene] weight ratio as defined by the following formula,

${\%\mspace{14mu}{{Reduced}\mspace{14mu}\left\lbrack \frac{\alpha - {olefin}}{ethylene} \right\rbrack}} = {{100 \times \left\{ \frac{\left( \frac{\alpha - {olefin}}{ethylene} \right)^{A} - \left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}}{\left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}} \right\}} \leq {{- 70}\%}}$ wherein (α-olefin/ethylene)^(A) is calculated by dividing the weight of the α-olefin added to the first reactor by the weight of ethylene added to the first reactor, wherein a first ethylene interpolymer is produced having “a target density” using a first homogeneous catalyst formulation, and; (α-olefin/ethylene)^(C) is calculated by dividing the weight of the α-olefin added to the first reactor by the weight of the ethylene added to the first reactor, wherein a control ethylene interpolymer having the target density is produced by replacing the first homogeneous catalyst formulation with a third homogeneous catalyst formulation, and/or; 2) the first ethylene interpolymer at least a 5% improved weight average molecular weight as defined by the following formula % Improved M _(w)=100%×(M _(w) ^(A) −M _(w) ^(C))/M _(w) ^(C)≥5% wherein M_(w) ^(A) is a weight average molecular weight of the first ethylene interpolymer and M_(w) ^(C) is a weight average molecular weight of a comparative ethylene interpolymer; wherein said comparative ethylene interpolymer is produced in the first reactor by replacing the first homogeneous catalyst formulation with the third homogeneous catalyst formulation.

Embodiments of the improved continuous solution polymerization process are shown in FIG. 2. FIG. 2 is not to be construed as limiting, it being understood, that embodiments are not limited to the precise arrangement of, or the number of, vessels shown.

In an embodiment of the continuous solution polymerization process, process solvent, monomer(s) and a catalyst formulation are continuously fed to a reactor wherein the desired ethylene interpolymer is formed in solution. In FIG. 2, process solvent 1, ethylene 2 and optional α-olefin 3 are combined to produce reactor feed stream RF1 which flows into reactor 11 a. In FIG. 2 optional streams, or optional embodiments, are denoted with dotted lines. It is not particularly important that combined reactor feed stream RF1 be formed; i.e. reactor feed streams can be combined in all possible combinations, including an embodiment where streams 1 through 3 are independently injected into reactor 11 a. Optionally hydrogen may be injected into reactor 11 a through stream 4; hydrogen may be added to control (reduce) the molecular weight of the first ethylene interpolymer produced in reactor 11 a. Reactor 11 a is continuously stirred by stirring assembly 11 b which includes a motor external to the reactor and an agitator within the reactor. In the art, such a reactor is frequently called a CSTR (Continuously Stirred Tank Reactor).

A first homogeneous catalyst formulation is injected into reactor 11 a through stream 5 e. An embodiment of the first homogeneous catalyst formulation is a bridged metallocene catalyst formulation. The bridged metallocene catalyst formulation (described above) was employed in reactor 11 a to produce all of the Examples in this disclosure. In contrast, a third homogeneous catalyst formulation was employed in reactor 11 a to produce all of the Comparatives in this disclosure. As described above, one embodiment of the third homogeneous catalyst formulation was an unbridged single site catalyst formulation.

Referring to FIG. 2, the bridged metallocene catalyst formulation was prepared by combining: stream 5 a, containing a component P^(A1) dissolved in a catalyst component solvent; stream 5 b, containing a component M^(A1) dissolved in a catalyst component solvent; stream 5 c, containing a bulky ligand-metal complex component A1 dissolved in a catalyst component solvent, and; stream 5 d, containing component B^(A1) dissolved in a catalyst component solvent. The bridged metallocene catalyst formulation was then injected into reactor 11 a via process stream 5 e. Any combination of the streams employed to prepare and deliver the bridged metallocene catalyst formulation may be heated or cooled, i.e. streams 5 a through 5 e.

The “R1 catalyst inlet temperature”, defined as the temperature of the solution containing the bridged metallocene catalyst formulation (stream 5 e) prior to injection into reactor 11 a, was controlled. In some cases the upper temperature limit on the R1 catalyst inlet temperature may be about 180° C., in other cases about 160° C. and in still other cases about 150° C., and; in some cases the lower temperature limit on the R1 catalyst inlet temperature may be about 80° C., in other cases 100° C. and in still other cases about 120° C. In still other cases the upper temperature limit on the R1 catalyst inlet temperature may be about 70° C., in other cases about 60° C. and in still other cases about 50° C., and; in some cases the lower temperature limit on the R1 catalyst inlet temperature may be about 0° C., in other cases 10° C. and in still other cases about 20° C.

Each catalyst component was dissolved in a catalyst component solvent. The catalyst component solvent used for each catalyst component may be the same or different. Catalyst component solvents are selected such that the combination of catalyst components does not produce a precipitate in any process stream; for example, precipitation of a catalyst components in stream 5 e. The optimization of the catalyst formulations are described below.

Reactor 11 a produces a first exit stream, stream 11 c, containing the first ethylene interpolymer dissolved in process solvent, as well as unreacted ethylene, unreacted α-olefins (if present), unreacted hydrogen (if present), active first homogeneous catalyst, deactivated catalyst, residual catalyst components and other impurities (if present). Melt index ranges and density ranges of the first ethylene interpolymer produced are described below.

The continuous solution polymerization process shown in FIG. 2 includes two embodiments where reactors 11 a and 12 a can be operated in series or parallel modes. In series mode 100% of stream 11 c (the first exit stream) passes through flow controller 11 d forming stream 11 e which enters reactor 12 a. In contrast, in parallel mode 100% of stream 11 c passes through flow controller 11 f forming stream 11 g. Stream 11 g by-passes reactor 12 a and is combined with stream 12 c (the second exit stream) forming stream 12 d (the third exit stream).

Fresh reactor feed streams are injected into reactor 12 a; process solvent 6, ethylene 7 and optional α-olefin 8 are combined to produce reactor feed stream RF2. It is not important that stream RF2 is formed; i.e. reactor feed streams can be combined in all possible combinations, including independently injecting each stream into the reactor. Optionally hydrogen may be injected into reactor 12 a through stream 9 to control (reduce) the molecular weight of the second ethylene interpolymer. Reactor 12 a is continuously stirred by stirring assembly 12 b which includes a motor external to the reactor and an agitator within the reactor.

A second homogeneous catalyst formulation was injected in reactor 12 a through stream 10 e, one embodiment of the second homogeneous catalyst formulation is an unbridged single site catalyst formulation which produces a second ethylene interpolymer in reactor 12 a. The components that comprise the unbridged single site catalyst formulation are introduced through streams 10 a, 10 b, 10 c and 10 d. The unbridged single site catalyst formulation was prepared by combining: stream 10 a, containing a component P^(C1) dissolved in a catalyst component solvent; stream 10 b, containing a component M^(C1) dissolved in a catalyst component solvent; stream 10 c, containing a bulky ligand-metal complex component C1 dissolved in a catalyst component solvent, and; stream 10 d, containing component B^(C1) dissolved in a catalyst component solvent. The unbridged single site catalyst formulation was then injected into reactor 12 a via process stream 10 e. Any combination of the streams employed to prepare and deliver the unbridged single site catalyst formulation may be heated or cooled, i.e. streams 10 a through 10 e. Each catalyst component was dissolved in a catalyst component solvent. The catalyst component solvents used to synthesize the unbridged single site catalyst formulation may be the same or different. Catalyst component solvents are selected such that the combination of catalyst components does not produce a precipitate in any process stream; for example, precipitation of a catalyst components in stream 10 e. The optimization of the catalyst formulations are described below. The “R2 catalyst inlet temperature”, defined as the temperature of the solution containing the bridged metallocene catalyst formulation (stream 10 e) prior to injection into reactor 12 a, was controlled. In some cases the upper temperature limit on the R2 catalyst inlet temperature may be about 70° C., in other cases about 60° C. and in still other cases about 50° C., and; in some cases the lower temperature limit on the R2 catalyst inlet temperature may be about 0° C., in other cases 10° C. and in still other cases about 20° C. Any combination of the streams employed to prepare and deliver the second homogeneous catalyst formulation to the second reactor (R2) may be heated or cooled, i.e. streams 10 a through 10 e.

Injection of the second homogeneous catalyst formulation into reactor 12 a produces a second ethylene interpolymer and a second exit stream 12 c.

If reactors 11 a and 12 a are operated in a series mode, the second exit stream 12 c contains the second ethylene interpolymer and the first ethylene interpolymer dissolved in process solvent; as well as unreacted ethylene, unreacted α-olefins (if present), unreacted hydrogen (if present), active catalysts, deactivated catalysts, catalyst components and other impurities (if present). Optionally the second exit stream 12 c is deactivated by adding a catalyst deactivator A from catalyst deactivator tank 18A forming a deactivated solution A, stream 12 e; in this case, FIG. 2 defaults to a dual reactor solution process. If the second exit stream 12 c is not deactivated the second exit stream enters tubular reactor 17. Catalyst deactivator A is discussed below.

If reactors 11 a and 12 a are operated in parallel mode, the second exit stream 12 c contains the second ethylene interpolymer dissolved in process solvent. The second exit stream 12 c is combined with stream 11 g forming a third exit stream 12 d, the latter contains the second ethylene interpolymer and the first ethylene interpolymer dissolved in process solvent; as well as unreacted ethylene, unreacted α-olefins (if present), unreacted hydrogen (if present), active catalyst, deactivated catalyst, catalyst components and other impurities (if present). Optionally the third exit stream 12 d is deactivated by adding catalyst deactivator A from catalyst deactivator tank 18A forming deactivated solution A, stream 12 e; in this case, FIG. 2 defaults to a dual reactor solution process. If the third exit stream 12 d is not deactivated the third exit stream 12 d enters tubular reactor 17.

The term “tubular reactor” is meant to convey its conventional meaning, namely a simple tube; wherein the length/diameter (L/D) ratio is at least 10/1. Optionally, one or more of the following reactor feed streams may be injected into tubular reactor 17; process solvent 13, ethylene 14 and α-olefin 15. As shown in FIG. 2, streams 13, 14 and 15 may be combined forming reactor feed stream RF3 and the latter is injected into reactor 17. It is not particularly important that stream RF3 be formed; i.e. reactor feed streams can be combined in all possible combinations. Optionally hydrogen may be injected into reactor 17 through stream 16.

Optionally, the first and/or the second homogeneous catalyst formulations may be injected into reactor 17 (not shown in FIG. 2). This could be accomplished by feeding a portion of stream 5 e to reactor 17 and/or feeding a portion of stream 10 e to reactor 17. Alternatively, a non-limiting embodiment includes a fifth homogenous catalyst assembly (not shown in FIG. 2) that manufactures and injects a fifth homogeneous catalyst formulation into reactor 17. The fifth homogeneous catalyst assembly refers to a combination of tanks, conduits and flow controllers similar to 5 a through 5 e shown in FIG. 2 (i.e. the first homogeneous catalyst assembly) or similar to 10 a through 10 e shown in FIG. 2 (i.e. the second homogeneous catalyst assembly). The fifth homogeneous catalyst formulation may be the first homogeneous catalyst formulation, the second homogeneous catalyst formulation or the fourth homogeneous catalyst formulation.

Optionally, a heterogeneous catalyst formulation may be injected into reactor 17. One embodiment of a heterogeneous catalyst formulation includes an in-line Ziegler-Natta catalyst formulation. FIG. 2 illustrates an in-line heterogeneous catalyst assembly, defined by conduits and flow controllers 34 a through 34 h, that manufactures and injects an in-line Ziegler-Natta catalyst formulation into tubular reactor 17.

The in-line heterogeneous catalyst assembly generates a high activity catalyst by optimizing hold-up-times and the following molar ratios: (aluminum alkyl)/(magnesium compound), (chloride compound)/(magnesium compound), (alkyl aluminum co-catalyst/(metal compound, and (aluminum alkyl)/(metal compound). To be clear: stream 34 a contains a binary blend of magnesium compound (component (v)) and aluminum alkyl (component (ix)) in process solvent; stream 34 b contains a chloride compound (component (vi)) in process solvent; stream 34 c contains a metal compound (component (vii)) in process solvent, and; stream 34 d contains an alkyl aluminum co-catalyst (component (viii)) in process solvent. To produce a highly active in-line Ziegler-Natta catalyst (highly active in olefin polymerization), the (chloride compound)/(magnesium compound) molar ratio is optimized. The upper limit on the (chloride compound)/(magnesium compound) molar ratio may be about 4, in some cases about 3.5 and is other cases about 3.0. The lower limit on the (chloride compound)/(magnesium compound) molar ratio may be about 1.0, in some cases about 1.5 and in other cases about 1.9. The time between the addition of the chloride compound and the addition of the metal compound (component (vii)) via stream 34 c is controlled; hereinafter HUT-1 (the first Hold-Up-Time). HUT-1 is the time for streams 34 a and 34 b to equilibrate and form a magnesium chloride support. The upper limit on HUT-1 may be about 70 seconds, in some cases about 60 seconds and is other cases about 50 seconds. The lower limit on HUT-1 may be about 5 seconds, in some cases about 10 seconds and in other cases about 20 seconds. HUT-1 is controlled by adjusting the length of the conduit between stream 34 b injection port and stream 34 c injection port, as well as controlling the flow rates of streams 34 a and 34 b. The time between the addition of component (vii) and the addition of the alkyl aluminum co-catalyst, component (viii), via stream 34 d is controlled; hereinafter HUT-2 (the second Hold-Up-Time). HUT-2 is the time for the magnesium chloride support and stream 34 c to react and equilibrate. The upper limit on HUT-2 may be about 50 seconds, in some cases about 35 seconds and is other cases about 25 seconds. The lower limit on HUT-2 may be about 2 seconds, in some cases about 6 seconds and in other cases about 10 seconds. HUT-2 is controlled by adjusting the length of the conduit between stream 34 c injection port and stream 34 d injection port, as well as controlling the flow rates of streams 34 a, 34 b and 34 c. The quantity of the alkyl aluminum co-catalyst added is optimized to produce an efficient catalyst; this is accomplished by adjusting the (alkyl aluminum co-catalyst)/(metal compound) molar ratio, or (viii)/(vii) molar ratio. The upper limit on the (alkyl aluminum co-catalyst)/(metal compound) molar ratio may be about 10, in some cases about 7.5 and is other cases about 6.0. The lower limit on the (alkyl aluminum co-catalyst)/(metal compound) molar ratio may be 0, in some cases about 1.0 and in other cases about 2.0. In addition, the time between the addition of the alkyl aluminum co-catalyst and the injection of the in-line Ziegler-Natta catalyst formulation into reactor 17 is controlled; hereinafter HUT-3 (the third Hold-Up-Time). HUT-3 is the time for stream 34 d to intermix and equilibrate to form the in-line Ziegler Natta catalyst formulation. The upper limit on HUT-3 may be about 15 seconds, in some cases about 10 seconds and is other cases about 8 seconds. The lower limit on HUT-3 may be about 0.5 seconds, in some cases about 1 seconds and in other cases about 2 seconds. HUT-3 is controlled by adjusting the length of the conduit between stream 34 d injection port and the catalyst injection port in reactor 17, and by controlling the flow rates of streams 34 a through 34 d. As shown in FIG. 2, optionally, 100% of stream 34 d, the alkyl aluminum co-catalyst, may be injected directly into reactor 17 via stream 34 h. Optionally, a portion of stream 34 d may be injected directly into reactor 17 via stream 34 h and the remaining portion of stream 34 d injected into reactor 17 via stream 34 f. In FIG. 2, the in-line heterogeneous catalyst assembly supplies 100% of the catalyst to reactor 17. Any combination of the streams that comprise the in-line heterogeneous catalyst assembly may be heated or cooled, i.e. streams 34 a-34 e and 34 h; in some cases the upper temperature limit of streams 34 a-34 e and 34 h may be about 90° C., in other cases about 80° C. and in still other cases about 70° C. and; in some cases the lower temperature limit may be about 20° C.; in other cases about 35° C. and in still other cases about 50° C. The quantity of the in-line Ziegler-Natta catalyst formulation added to reactor 17 was expressed as the parts-per-million (ppm) of metal compound (component (vii)) in the reactor solution. The upper limit on component (vii) in reactor 17 may be about 10 ppm, in some cases about 8 ppm and in other cases about 6 ppm; while the lower limit may be about 0.5 ppm, in other cases about 1 ppm and in still other cases about 2 ppm. The (aluminum alkyl)/(metal compound) molar ratio in reactor 17, or the (ix)/(vii) molar ratio, is also controlled. The upper limit on the (aluminum alkyl)/(metal compound) molar ratio in the reactor may be about 2, in some cases about 1.5 and is other cases about 1.0. The lower limit on the (aluminum alkyl)/(metal compound) molar ratio may be about 0.05, in some cases about 0.075 and in other cases about 0.1.

Optionally, an additional embodiment of a heterogeneous catalyst formulation includes a batch Ziegler-Natta catalyst formulation. FIG. 2 illustrates a batch heterogeneous catalyst assembly, defined by conduits and flow controllers 90 a through 90 f. The batch heterogeneous catalyst assembly manufactures and injects the batch Ziegler-Natta catalyst formulation, or a batch Ziegler-Natta procatalyst, into tubular reactor 17.

Processes to prepare batch Ziegler-Natta procatalysts are well known to those skilled in the art. A non-limiting formulation useful in the disclosed polymerization process may be prepared as follows. A batch Ziegler-Natta procatalyst may be prepared by sequentially added the following components to a stirred mixing vessel: (a) a solution of a magnesium compound (an equivalent term for the magnesium compound is “component (v)”); (b) a solution of a chloride compound (an equivalent term for the chloride compound is “component (vi)”; (c) optionally a solution of an aluminum alkyl halide, and; (d) a solution of a metal compound (an equivalent term for the metal compound is “component (vii)”). Suitable, non-limiting examples of aluminum alkyl halides are defined by the formula (R⁶)_(v)AIX_(3-v); wherein the R⁶ groups may be the same or different hydrocarbyl group having from 1 to 10 carbon atoms, X represents chloride or bromide, and; v is 1 or 2. Suitable, non-limiting examples of the magnesium compound, the chloride compound and the metal compound were described earlier in this disclosure. Suitable solvents within which to prepare the procatalyst include linear or branched C₅ to C₁₂ alkanes or mixtures thereof. Individual mixing times and mixing temperatures may be used in each of steps (a) through (d). The upper limit on mixing temperatures for steps (a) through (d) in some case may be 160° C., in other cases 130° C. and in still other cases 100° C. The lower limit on mixing temperatures for steps (a) through (d) in some cases may be 10° C., in other cases 20° C. and in still other cases 30° C. The upper limit on mixing time for steps (a) through (d) in some case may be 6 hours, in other cases 3 hours and in still other cases 1 hour. The lower limit on mixing times for steps (a) through (d) in some cases may be 1 minute, in other cases 10 minutes and in still other cases 30 minutes. Batch Ziegler-Natta procatalyst may have various catalyst component mole ratios. The upper limit on the (chloride compound)/(magnesium compound) molar ratio in some cases may be about 3, in other cases about 2.7 and is still other cases about 2.5; the lower limit in some cases may be about 2.0, in other cases about 2.1 and in still other cases about 2.2. The upper limit on the (magnesium compound)/(metal compound) molar ratio in some cases may be about 10, in other cases about 9 and in still other cases about 8; the lower limit in some cases may be about 5, in other cases about 6 and in still other cases about 7. The upper limit on the (aluminum alkyl halide)/(magnesium compound) molar ratio in some cases may be about 0.5, in other cases about 0.4 and in still other cases about 0.3; the lower limit in some cases may be 0, in other cases about 0.1 and in still other cases about 0.2. An active batch Ziegler-Natta catalyst formulation is formed when the procatalyst is combined with an alkyl aluminum co-catalyst. Suitable co-catalysts were described earlier in this disclosure. The procatalyst may be activated external to the reactor or in the reactor; in the latter case, the procatalyst and an appropriate amount of alkyl aluminum co-catalyst are independently injected R2 and optionally R3.

Once prepared the batch Ziegler-Natta procatalyst is pumped to procatalyst storage tank 90 a shown in FIG. 2. Tank 90 a may, or may not, be agitated. Storage tank 90 c contains an alkyl,aluminum co-catalyst. A batch Ziegler Natta catalyst formulation stream 90 e, that is efficient in converting olefins to polyolefins, is formed by combining the batch Ziegler Natta procatalyst stream 90 b with alkyl aluminum co-catalyst stream 90 d. Stream 90 e is optionally injected into reactor 17, wherein an optional third ethylene interpolymer may be formed. FIG. 2 includes additional embodiments where: (a) the batch Ziegler-Natta procatalyst is injected directly into reactor 17 through stream 90 e and the procatalyst is activated inside reactor 17 by injecting 100% of the aluminum co-catalyst directly into rector 17 via stream 90 f, or; (b) a portion of the aluminum co-catalyst may flow through stream 90 e with the remaining portion flowing through stream 90 f. Any combination of tanks or streams 90 a through 90 f may be heated or cooled. The time between the addition of the alkyl aluminum co-catalyst and the injection of the batch Ziegler-Natta catalyst formulation into reactor 17 is controlled. Referring to FIG. 2, HUT-4 is the time for stream 90 d to intermix and equilibrate with stream 90 b (batch Ziegler-Natta procatalyst) to form the batch Ziegler Natta catalyst formulation prior to injection into reactor 17 via in stream 90 e. The upper limit on HUT-4 may be about 300 seconds, in some cases about 200 seconds and in other cases about 100 seconds. The lower limit on HUT-4 may be about 0.1 seconds, in some cases about 1 seconds and in other cases about 10 seconds. The quantity of batch Ziegler-Natta procatalyst or batch Ziegler-Natta catalyst formulation added to reactor 17 was expressed the parts-per-million (ppm) of metal compound (component (vii)) in the reactor solution. The upper limit on component (vii) may be about 10 ppm, in some cases about 8 ppm and in other cases about 6 ppm; while the lower limit may be about 0.5 ppm, in some cases about 1 ppm and in other cases about 2 ppm. The quantity of the alkyl aluminum co-catalyst added to reactor 17 is optimized to produce an efficient catalyst; this is accomplished by adjusting the (alkyl aluminum co-catalyst)/(metal compound) molar ratio. The upper limit on the (alkyl aluminum co-catalyst)/(metal compound) molar ratio may be about 10, in some cases about 8.0 and is other cases about 6.0. The lower limit on the (alkyl aluminum co-catalyst)/(metal compound) molar ratio may be 0.5, in some cases about 0.75 and in other cases about 1.

The quantity of batch Ziegler-Natta procatalyst produced and/or the size to procatalyst storage tank 90 a is not particularly important with respect to this disclosure. However, the large quantity of procatalyst produced allows one to operate the continuous solution polymerization plant for an extended period of time: the upper limit on this time in some cases may be about 3 months, in other cases for about 2 months and in still other cases for about 1 month; the lower limit on this time in some cases may be about 1 day, in other cases about 1 week and in still other cases about 2 weeks.

In reactor 17 a third ethylene interpolymer may, or may not, form. A third ethylene interpolymer will not form if catalyst deactivator A is added upstream of reactor 17 via catalyst deactivator tank 18A (as shown in FIG. 2). In contrast, A third ethylene interpolymer will be formed if catalyst deactivator B is added downstream of reactor 17 via catalyst deactivator tank 18B.

The optional third ethylene interpolymer produced in reactor 17 may be formed using a variety of operational modes; with the proviso that catalyst deactivator A is not added upstream of reactor 17. Non-limiting examples of operational modes include: (a) residual ethylene, residual optional α-olefin and residual active catalyst entering reactor 17 react to form the optional third ethylene interpolymer, or; (b) fresh process solvent 13, fresh ethylene 14 and optionally fresh α-olefin 15 are added to reactor 17 and the residual active catalyst entering reactor 17 forms the optional third ethylene interpolymer, or; (c) a fifth homogeneous catalyst formulation is added to reactor 17 to polymerize residual ethylene and residual optional α-olefin to form the third ethylene interpolymer, or; (d) an in-line Ziegler-Natta catalyst formulation is added to reactor 17 via stream 34 e (FIG. 2) to polymerize residual ethylene and residual optional α-olefin to form the third ethylene interpolymer, or; (e) a batch Ziegler-Natta catalyst formulation is added to reactor 17 via stream 90 e (FIG. 2) to polymerize residual ethylene and residual optional α-olefin to form the third ethylene interpolymer, or; (d) fresh process solvent (stream 13), ethylene (stream 14), optional α-olefin (stream 15) and a fifth homogeneous catalyst formulation, or an in-line Ziegler-Natta catalyst formulation or a batch Ziegler-Natta catalyst formulation are added to reactor 17 to form the third ethylene interpolymer. Optionally fresh hydrogen (stream 16) may be added to control (reduce) the molecular weight of the third optional ethylene interpolymer.

In series mode, Reactor 17 produces a third exit stream 17 b containing the first ethylene interpolymer, the second ethylene interpolymer and optionally a third ethylene interpolymer. As shown in FIG. 2, catalyst deactivator B may be added to the third exit stream 17 b via catalyst deactivator tank 18B producing a deactivated solution B, stream 19; with the proviso that catalyst deactivator B is not added if catalyst deactivator A was added upstream of reactor 17. Deactivated solution B may also contain unreacted ethylene, unreacted optional α-olefin, unreacted optional hydrogen and impurities if present. As indicated above, if catalyst deactivator A was added, deactivated solution A (stream 12 e) exits tubular reactor 17 as shown in FIG. 2.

In parallel mode operation, reactor 17 produces a fourth exit stream 17 b containing the first ethylene interpolymer, the second ethylene interpolymer and optionally a third ethylene interpolymer. As described above, in parallel mode stream 12 d was the third exit stream. As shown in FIG. 2, in parallel mode catalyst deactivator B is added to the fourth exit stream 17 b via catalyst deactivator tank 18B producing a deactivated solution B, stream 19; with the proviso that catalyst deactivator B is not added if catalyst deactivator A was added upstream of reactor 17.

In FIG. 2, deactivated solution A (stream 12 e) or B (stream 19) passes through pressure let down device 20, heat exchanger 21 and optionally a passivator was added via tank 22 forming a passivated solution stream 23; the passivator is described below. The passivator was added, and stream 23 was formed, only if a heterogeneous catalyst formulation was added to reactor 17. Stream 19, or optional stream 23, passes through pressure let down device 24 and entered a first vapor/liquid separator 25. Hereinafter, “V/L” is equivalent to vapor/liquid. Two streams were formed in the first V/L separator: a first bottom stream 27 comprising a solution that was rich in ethylene interpolymers and also contains residual ethylene, residual optional α-olefins and catalyst residues, and; a first gaseous overhead stream 26 comprising ethylene, process solvent, optional α-olefins, optional hydrogen, oligomers and light-end impurities if present.

The first bottom stream entered a second V/L separator 28. In the second V/L separator two streams were formed: a second bottom stream 30 comprising a solution that was richer in ethylene interpolymer and leaner in process solvent relative to the first bottom stream 27, and; a second gaseous overhead stream 29 comprising process solvent, optional α-olefins, ethylene, oligomers and light-end impurities if present.

The second bottom stream 30 flowed into a third V/L separator 31. In the third V/L separator two streams were formed: a product stream 33 comprising an ethylene interpolymer product, deactivated catalyst residues and less than 5 weight % of residual process solvent, and; a third gaseous overhead stream 32 comprised essentially of process solvent, optional α-olefins and light-end impurities if present.

Product stream 33 proceeded to polymer recovery operations. Non-limiting examples of polymer recovery operations include one or more gear pump, single screw extruder or twin screw extruder that forces the molten ethylene interpolymer product through a pelletizer. A devolatilizing extruder may be used to remove small amounts of residual process solvent and optional α-olefin, if present. Once pelletized the solidified ethylene interpolymer product is typically dried and transported to a product silo.

The first, second and third gaseous overhead streams shown in FIG. 2 (streams 26, 29 and 32, respectively) were sent to a distillation column where solvent, ethylene and optional α-olefin were separated for recycling, or; the first, second and third gaseous overhead streams were recycled to the reactors, or; a portion of the first, second and third gaseous overhead streams were recycled to the reactors and the remaining portion was sent to a distillation column.

Comparatives

In this disclosure Comparative ethylene interpolymer samples were produced by replacing the first homogeneous catalyst formulation (used in the first reactor (R1)) with a third homogeneous catalyst formulation. One embodiment of the first homogeneous catalyst formulation was a bridged metallocene catalyst formulation containing component A (represented by Formula (I)) and one embodiment of the third homogeneous catalyst formulation was an unbridged single site catalyst formulation containing component C (represented by Formula (II)), as fully described above.

To be more clear, referring to FIG. 2, the third homogeneous catalyst formulation or the unbridged single site catalyst formulation was prepared by combining: stream 5 a, containing component P dissolved in a catalyst component solvent; stream 5 b, containing component M dissolved in a catalyst component solvent; stream 5 c, containing component C dissolved in a catalyst component solvent, and; stream 5 d, containing component B dissolved in a catalyst component solvent. The third homogeneous catalyst formulation was then injected into reactor 11 a via process stream 5 e producing a comparative first ethylene interpolymer in reactor 11 a. The “R1 catalyst inlet temperature” was controlled. In the case of the unbridged singe site catalyst formulation the upper temperature limit on the R1 catalyst inlet temperature may be about 70° C., in other cases about 60° C. and in still other cases about 50° C., and; in some cases the lower temperature limit on the R1 catalyst inlet temperature may be about 0° C., in other cases about 10° C. and in still other cases about 20° C. The same catalyst component solvents were used to prepare both the first and third homogeneous catalyst formulations.

For all Comparative ethylene interpolymer products disclosed, the second homogeneous catalyst formulation (described above) was injected into reactor 12 a (R2), wherein the second ethylene interpolymer was formed. Comparative ethylene interpolymer products were an in-situ solution blend of: 1) the comparative first ethylene interpolymer (produced with the third homogeneous catalyst formulation); 2) the second ethylene interpolymer, and; 3) optionally the third ethylene interpolymer.

Optimization of Homogeneous Catalyst Formulations

Referring to the first homogeneous catalyst formulation, one embodiment being the bridged metallocene catalyst formulation, a highly active formulation was produced by optimizing the proportion of each of the four catalyst components: component A, component M, component B and component P. The term “highly active” means the catalyst formulation is very efficient in converting olefins to polyolefins. In practice the optimization objective is to maximize the following ratio: (pounds of ethylene interpolymer product produced)/(pounds of catalyst consumed). The quantity of the bulky ligand-metal complex, component A, added to R1 was expressed as the parts per million (ppm) of component A in the total mass of the solution in R1, i.e. “R1 catalyst (ppm)” as recited in Table 4A. The upper limit on the ppm of component A may be about 5, in some cases about 3 and is other cases about 2. The lower limit on the ppm of component A may be about 0.02, in some cases about 0.05 and in other cases about 0.1.

The proportion of catalyst component B, the ionic activator, added to R1 was optimized by controlling the (ionic activator)/(component A) molar ratio, ([B]/[A]), in the R1 solution. The upper limit on the R1 ([B]/[A]) may be about 10, in some cases about 5 and in other cases about 2. The lower limit on R1 ([B]/[A]) may be about 0.3, in some cases about 0.5 and in other cases about 1.0. The proportion of catalyst component M was optimized by controlling the (alumoxane)/(component A) molar ratio, ([M]/[A]), in the R1 solution. The alumoxane co-catalyst was generally added in a molar excess relative to component A. The upper limit on R1 ([M]/[A]), may be about 300, in some cases about 200 and is other cases about 100. The lower limit on R1 ([M]/[A]), may be about 1, in some cases about 10 and in other cases about 30. The addition of catalyst component P (the hindered phenol) to R1 is optional. If added, the proportion of component P was optimized by controlling the (hindered phenol)/(alumoxane), ([P]/[M]), molar ratio in R1. The upper limit on R1 ([P]/[M]) may be about 1, in some cases about 0.75 and in other cases about 0.5. The lower limit on R1 ([P]/[M]) may be 0.0, in some cases about 0.1 and in other cases about 0.2.

Referring to the second homogeneous catalyst formulation, one embodiment being the unbridged single site catalyst formulation, a highly active formulation was produced by optimizing the proportion of each of the four catalyst components: component C, component M, component B and component P. Catalyst components M, B and P were independently selected for the second homogeneous catalyst formulation, relative to the first homogeneous catalyst formulation. To be more clear, components M, B and P in the second homogeneous catalyst formulation may be the same chemical compound, or a different chemical compound, that was used to formulate the first homogeneous catalyst formulation.

The quantity of the bulky ligand metal complex, component C, added to R2 was expressed as the parts per million (ppm) of component C in the total mass of the solution in R2, i.e. “R2 catalyst (ppm)” shown in Table 4A. The upper limit on the R2 ppm of component C may be about 5, in some cases about 3 and is other cases about 2. The lower limit on the R2 ppm of component C may be about 0.02, in some cases about 0.05 and in other cases about 0.1. The proportion of catalyst component B, the ionic activator, added to R2 was optimized by controlling the (ionic activator)/(bulky ligand-metal complex) molar ratio, ([B]/[C]), in the R2 solution. The upper limit on R2 ([B]/[C]) may be about 10, in some cases about 5 and in other cases about 2. The lower limit on R2 ([B]/[C]) may be about 0.3, in some cases about 0.5 and in other cases about 1.0. The proportion of catalyst component M was optimized by controlling the (alumoxane)/(bulky ligand-metal complex) molar ratio, ([M]/[C]), in the R2 solution. The alumoxane co-catalyst was generally added in a molar excess relative to the bulky ligand-metal complex. The upper limit on the ([M]/[C]) molar ratio may be about 1000, in some cases about 500 and is other cases about 200. The lower limit on the ([M]/[C]) molar ratio may be about 1, in some cases about 10 and in other cases about 30. The addition of catalyst component P to R2 is optional. If added, the proportion of component P was optimized by controlling the (hindered phenol)/(alumoxane) molar ratio, ([P]/[M]), in R2. The upper limit on the R2 ([P]/[M]) molar ratio may be about 1.0, in some cases about 0.75 and in other cases about 0.5. The lower limit on the R2 ([P]/[M]) molar ratio may be 0.0, in some cases about 0.1 and in other cases about 0.2.

In the case of the third homogeneous catalyst formulation that was used to synthesize Comparative ethylene interpolymer products a highly active formulation was produced by optimizing the proportion of each of the four catalyst components: component C, component M, component B and component P; in a similar fashion to that described above for the second homogeneous catalyst formulation.

Additional Solution Polymerization Process Parameters

In the continuous solution processes embodiments shown in FIG. 2 a variety of solvents may be used as the process solvent; non-limiting examples include linear, branched or cyclic C₅ to C₁₂ alkanes. Non-limiting examples of α-olefins include 1-propene, 1-butene, 1-pentene, 1-hexene and 1-octene. Suitable catalyst component solvents include aliphatic and aromatic hydrocarbons. Non-limiting examples of aliphatic catalyst component solvents include linear, branched or cyclic C₅₋₁₂ aliphatic hydrocarbons, e.g. pentane, methyl pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, hydrogenated naphtha or combinations thereof. Non-limiting examples of aromatic catalyst component solvents include benzene, toluene (methylbenzene), ethylbenzene, o-xylene (1,2-dimethylbenzene), m-xylene (1,3-dimethylbenzene), p-xylene (1,4-dimethylbenzene), mixtures of xylene isomers, hemellitene (1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), mixtures of trimethylbenzene isomers, prehenitene (1,2,3,4-tetramethylbenzene), durene (1,2,3,5-tetramethylbenzene), mixtures of tetramethylbenzene isomers, pentamethylbenzene, hexamethylbenzene and combinations thereof.

It is well known to individuals experienced in the art that reactor feed streams (solvent, monomer, α-olefin, hydrogen, catalyst formulation etc.) must be essentially free of catalyst deactivating poisons; non-limiting examples of poisons include trace amounts of oxygenates such as water, fatty acids, alcohols, ketones and aldehydes. Such poisons were removed from reactor feed streams using standard purification practices; non-limiting examples include molecular sieve beds, alumina beds and oxygen removal catalysts for the purification of solvents, ethylene and α-olefins, etc.

Referring to the first and second reactors in FIG. 2 any combination of the CSTR reactor feed streams may be heated or cooled: more specifically, streams 1-4 (reactor 11 a) and streams 6-9 (reactor 12 a). The upper limit on reactor feed stream temperatures may be about 90° C.; in other cases about 80° C. and in still other cases about 70° C. The lower limit on reactor feed stream temperatures may be about 0° C.; in other cases about 10° C. and in still other cases about 20° C.

Any combination of the streams feeding the tubular reactor may be heated or cooled; specifically, streams 13-16 in FIG. 2. In some cases, tubular reactor feed streams are tempered, i.e. the tubular reactor feed streams are heated to at least above ambient temperature. The upper temperature limit on the tubular reactor feed streams in some cases are about 200° C., in other cases about 170° C. and in still other cases about 140° C.; the lower temperature limit on the tubular reactor feed streams in some cases are about 60° C., in other cases about 90° C. and in still other cases about 120° C.; with the proviso that the temperature of the tubular reactor feed streams are lower than the temperature of the process stream that enters the tubular reactor.

In the embodiments shown in FIG. 2 the operating temperatures of the solution polymerization reactors (vessels 11 a (R1) and 12 a (R2)) can vary over a wide range. For example, the upper limit on reactor temperatures in some cases may be about 300° C., in other cases about 280° C. and in still other cases about 260° C.; and the lower limit in some cases may be about 80° C., in other cases about 100° C. and in still other cases about 125° C. The second reactor, reactor 12 a (R2), is operated at a higher temperature than the first reactor 11 a (R1). The maximum temperature difference between these two reactors (TR²−TR¹) in some cases is about 120° C., in other cases about 100° C. and in still other cases about 80° C.; the minimum (TR²−TR¹) in some cases is about 1° C., in other cases about 5° C. and in still other cases about 10° C. The optional tubular reactor, reactor 17 (R3), may be operated in some cases about 100° C. higher than R2; in other cases about 60° C. higher than R2, in still other cases about 10° C. higher than R2 and in alternative cases 0° C. higher, i.e. the same temperature as R2. The temperature within optional R3 may increase along its length. The maximum temperature difference between the inlet and outlet of R3 in some cases is about 100° C., in other cases about 60° C. and in still other cases about 40° C. The minimum temperature difference between the inlet and outlet of R3 is in some cases may be 0° C., in other cases about 3° C. and in still other cases about 10° C. In some cases R3 is operated an adiabatic fashion and in other cases R3 is heated.

The pressure in the polymerization reactors should be high enough to maintain the polymerization solution as a single phase solution and to provide the upstream pressure to force the polymer solution from the reactors through a heat exchanger and on to polymer recovery operations. Referring to the embodiments shown in FIG. 2, the operating pressure of the solution polymerization reactors can vary over a wide range. For example, the upper limit on reactor pressure in some cases may be about 45 MPag, in other cases about 30 MPag and in still other cases about 20 MPag; and the lower limit in some cases may be about 3 MPag, in other some cases about 5 MPag and in still other cases about 7 MPag.

Referring to the embodiments shown in FIG. 2, prior to entering the first V/L separator, stream 19, or optionally passivated stream 23 (if a heterogeneous catalyst formulation was employed in reactor 17) may have a maximum temperature in some cases of about 300° C., in other cases about 290° C. and in still other cases about 280° C.; the minimum temperature may be in some cases about 150° C., in other cases about 200° C. and in still other cases about 220° C. Immediately prior to entering the first V/L separator stream 19, or optionally passivated stream 23, may have a maximum pressure of about 40 MPag, in other cases about 25 MPag and in still cases about 15 MPag; the minimum pressure in some cases may be about 1.5 MPag, in other cases about 5 MPag and in still other cases about 6 MPag.

The first V/L separator (vessel 25 in FIG. 2) may be operated over a relatively broad range of temperatures and pressures. For example, the maximum operating temperature of the first V/L separator in some cases may be about 300° C., in other cases about 285° C. and in still other cases about 270° C.; the minimum operating temperature in some cases may be about 100° C., in other cases about 140° C. and in still other cases 170° C. The maximum operating pressure of the first V/L separator in some cases may be about 20 MPag, in other cases about 10 MPag and in still other cases about 5 MPag; the minimum operating pressure in some cases may be about 1 MPag, in other cases about 2 MPag and in still other cases about 3 MPag.

The second V/L separator (vessel 28 in FIG. 2) may be operated over a relatively broad range of temperatures and pressures. For example, the maximum operating temperature of the second V/L separator in some cases may be about 300° C., in other cases about 250° C. and in still other cases about 200° C.; the minimum operating temperature in some cases may be about 100° C., in other cases about 125° C. and in still other cases about 150° C. The maximum operating pressure of the second V/L separator in some cases may be about 1000 kPag, in other cases about 900 kPag and in still other cases about 800kPag; the minimum operating pressure in some cases may be about 10 kPag, in other cases about 20 kPag and in still other cases about 30 kPag.

The third V/L separator (vessel 31 in FIG. 2) may be operated over a relatively broad range of temperatures and pressures. For example, the maximum operating temperature of the third V/L separator in some cases may be about 300° C., in other cases about 250° C., and in still other cases about 200° C.; the minimum operating temperature in some cases may be about 100° C., in other cases about 125° C. and in still other cases about 150° C. The maximum operating pressure of the third V/L separator in some cases may be about 500 kPag, in other cases about 150 kPag and in still other cases about 100 kPag; the minimum operating pressure in some cases may be about 1 kPag, in other cases about 10 kPag and in still other cases 25 about kPag.

Embodiments of the continuous solution polymerization process shown in FIG. 2 show three V/L separators. However, continuous solution polymerization embodiments may include configurations comprising at least one V/L separator.

The ethylene interpolymer product produced in the continuous solution polymerization process may be recovered using conventional devolatilization systems that are well known to persons skilled in the art, non-limiting examples include flash devolatilization systems and devolatilizing extruders.

Any reactor shape or design may be used for reactor 11 a (R1) and reactor 12 a (R2) in FIG. 2; non-limiting examples include unstirred or stirred spherical, cylindrical or tank-like vessels, as well as tubular reactors or recirculating loop reactors. At commercial scale the maximum volume of R1 in some cases may be about 20,000 gallons (about 75,710 L), in other cases about 10,000 gallons (about 37,850 L) and in still other cases about 5,000 gallons (about 18,930 L). At commercial scale the minimum volume of R1 in some cases may be about 100 gallons (about 379 L), in other cases about 500 gallons (about 1,893 L) and in still other cases about 1,000 gallons (about 3,785 L). At pilot plant scales reactor volumes are typically much smaller, for example the volume of R1 at pilot scale could be less than about 2 gallons (less than about 7.6 L). In this disclosure the volume of reactor R2 was expressed as a percent of the volume of reactor R1. The upper limit on the volume of R2 in some cases may be about 600% of R1, in other cases about 400% of R1 and in still other cases about 200% of R1. For clarity, if the volume of R1 is 5,000 gallons and R2 is 200% the volume of R1, then R2 has a volume of 10,000 gallons. The lower limit on the volume of R2 in some cases may be about 50% of R1, in other cases about 100% of R1 and in still other cases about 150% of R1. In the case of continuously stirred tank reactors the stirring rate can vary over a wide range; in some cases from about 10 rpm to about 2000 rpm, in other cases from about 100 to about 1500 rpm and in still other cases from about 200 to about 1300 rpm. In this disclosure the volume of R3, the tubular reactor, was expressed as a percent of the volume of reactor R2. The upper limit on the volume of R3 in some cases may be about 500% of R2, in other cases about 300% of R2 and in still other cases about 100% of R2. The lower limit on the volume of R3 in some cases may be about 3% of R2, in other cases about 10% of R2 and in still other cases about 50% of R2.

The “average reactor residence time”, a commonly used parameter in the chemical engineering art, is defined by the first moment of the reactor residence time distribution; the reactor residence time distribution is a probability distribution function that describes the amount of time that a fluid element spends inside the reactor. The average reactor residence time can vary widely depending on process flow rates and reactor mixing, design and capacity. The upper limit on the average reactor residence time of the solution in R1 in some cases may be about 600 seconds, in other cases about 360 seconds and in still other cases about 180 seconds. The lower limit on the average reactor residence time of the solution in R1 in some cases may be about 10 seconds, in other cases about 20 seconds and in still other cases about 40 seconds. The upper limit on the average reactor residence time of the solution in R2 in some cases may be about 720 seconds, in other cases about 480 seconds and in still other cases about 240 seconds. The lower limit on the average reactor residence time of the solution in R2 in some cases may be about 10 seconds, in other cases about 30 seconds and in still other cases about 60 seconds. The upper limit on the average reactor residence time of the solution in R3 in some cases may be about 600 seconds, in other cases about 360 seconds and in still other cases about 180 seconds. The lower limit on the average reactor residence time of the solution in R3 in some cases may be about 1 second, in other cases about 5 seconds and in still other cases about 10 seconds.

Optionally, additional reactors (e.g. CSTRs, loops or tubes, etc.) could be added to the continuous solution polymerization process embodiments shown in FIG. 2. In this disclosure, the number of reactors was not particularly important; with the proviso that the continuous solution polymerization process comprises at least two reactors that employ a first homogeneous catalyst formulation and a second homogeneous catalyst, respectively.

In operating the continuous solution polymerization process embodiments shown in FIG. 2 the total amount of ethylene supplied to the process can be portioned or split between the three reactors R1, R2 and R3. This operational variable was referred to as the Ethylene Split (ES), i.e. “ES^(R1)”, “ES^(R2)” and “ES^(R3)” refer to the weight percent of ethylene injected in R1, R2 and R3, respectively; with the proviso that ES^(R1)+ES^(R2)+ES^(R3)=100%. This was accomplished by adjusting the ethylene flow rates in the following streams: stream 2 (R1), stream 7 (R2) and stream 14 (R3). The upper limit on ES^(R1) in some cases is about 60%, in other cases about 55% and in still other cases about 50%; the lower limit on ES^(R1) in some cases is about 5%, in other cases about 8% and in still other cases about 10%. The upper limit on ES^(R2) in some cases is about 95%, in other cases about 92% and in still other cases about 90%; the lower limit on ES^(R2) in some cases is about 20%, in other cases about 30% and in still other cases about 40%. The upper limit on ES^(R3) in some cases is about 30%, in other cases about 25% and in still other cases about 20%; the lower limit on ES^(R3) in some cases is 0%, in other cases about 5% and in still other cases about 10%.

In operating the continuous solution polymerization process embodiments shown in FIG. 2 the ethylene concentration in each reactor was also controlled. The ethylene concentration in reactor 1, hereinafter EC^(R1), is defined as the weight of ethylene in reactor 1 divided by the total weight of everything added to reactor 1; EC^(R2) and EC^(R3) are defined similarly. Ethylene concentrations in the reactors (EC^(R1) or EC^(R2) or EC^(R3)) in some cases may vary from about 7 weight percent (wt %) to about 25 wt %, in other cases from about 8 wt % to about 20 wt % and in still other cases from about 9 wt % to about 17 wt %.

In operating the continuous solution polymerization process embodiments shown in FIG. 2 the total amount of ethylene converted in each reactor was monitored. The term “Q^(R1)” refers to the percent of the ethylene added to R1 that was converted into an ethylene interpolymer by the catalyst formulation. Similarly Q^(R2) and Q^(R3) represent the percent of the ethylene added to R2 and R3 that was converted into ethylene interpolymer, in the respective reactor. Ethylene conversions can vary significantly depending on a variety of process conditions, e.g. catalyst concentration, catalyst formulation, impurities and poisons. The upper limit on both Q^(R1) and Q^(R2) in some cases is about 99%, in other cases about 95% and in still other cases about 90%; the lower limit on both Q^(R1) and Q^(R2) in some cases is about 65%, in other cases about 70% and in still other cases about 75%. The upper limit on Q^(R3) in some cases is about 99%, in other cases about 95% and in still other cases about 90%; the lower limit on Q^(R3) in some cases is 0%, in other cases about 5% and in still other cases about 10%. The term “Q^(T)” represents the total or overall ethylene conversion across the entire continuous solution polymerization plant; i.e. Q^(T)=100×[weight of ethylene in the interpolymer product]/([weight of ethylene in the interpolymer product]+[weight of unreacted ethylene]). The upper limit on Q^(T) in some cases is about 99%, in other cases about 95% and in still other cases about 90%; the lower limit on Q^(T) in some cases is about 75%, in other cases about 80% and in still other cases about 85%.

Optionally, α-olefin may be added to the continuous solution polymerization process. If added, α-olefin may be proportioned or split between R1, R2 and R3. This operational variable was referred to as the Comonomer Split (CS), i.e. “CS^(R1)”, “CS^(R2)” and “CS^(R3)” refer to the weight percent of α-olefin comonomer that is injected in R1, R2 and R3, respectively; with the proviso that CS^(R1)+CS^(R2)+CS^(R3)=100%. This is accomplished by adjusting α-olefin flow rates in the following streams: stream 3 (R1), stream 8 (R2) and stream 15 (R3). The upper limit on CS^(R1) in some cases is 100% (i.e. 100% of the α-olefin is injected into R1), in other cases about 95% and in still other cases about 90%. The lower limit on CS^(R1) in some cases is 0% (ethylene homopolymer produced in R1), in other cases about 5% and in still other cases about 10%. The upper limit on CS^(R2) in some cases is about 100% (i.e. 100% of the α-olefin is injected into reactor 2), in other cases about 95% and in still other cases about 90%. The lower limit on CS^(R2) in some cases is 0%, in other cases about 5% and in still other cases about 10%. The upper limit on CS^(R3) in some cases is 100%, in other cases about 95% and in still other cases about 90%. The lower limit on CS^(R3) in some cases is 0%, in other cases about 5% and in still other cases about 10%.

First Ethylene Interpolymer

The first ethylene interpolymer was synthesized using the first homogeneous catalyst formulation. One embodiment of the first homogeneous catalyst formulation was a bridged metallocene catalyst formulation. Referring to the embodiments shown in FIG. 2, if the optional α-olefin was not added to reactor 1 (R1), then the ethylene interpolymer produced in R1 was an ethylene homopolymer. If an α-olefin is added, the following weight ratio was one parameter to control the density of the first ethylene interpolymer: ((α-olefin)/(ethylene))^(R1). The upper limit on ((α-olefin)/(ethylene))^(R1) may be about 3; in other cases about 2 and in still other cases about 1. The lower limit on ((α-olefin)/(ethylene))^(R1) may be 0; in other cases about 0.25 and in still other cases about 0.5. Hereinafter, the symbol “σ¹” refers to the density of the first ethylene interpolymer produced in R1. The upper limit on σ¹ may be about 0.975 g/cm³; in some cases about 0.965 g/cm³ and; in other cases about 0.955 g/cm³. The lower limit on σ¹ may be about 0.855 g/cm³, in some cases about 0.865 g/cm³, and; in other cases about 0.875 g/cm³.

Methods to determine the CDBI₅₀ (Composition Distribution Branching Index) of an ethylene interpolymer are well known to those skilled in the art. The CDBI₅₀, expressed as a percent, was defined as the percent of the ethylene interpolymer whose comonomer composition is within 50% of the median comonomer composition. It is also well known to those skilled in the art that the CDBI₅₀ of ethylene interpolymers produced with homogeneous catalyst formulations are higher relative to the CDBI₅₀ of α-olefin containing ethylene interpolymers produced with heterogeneous catalyst formulations. The upper limit on the CDBI₅₀ of the first ethylene interpolymer may be about 98%, in other cases about 95% and in still other cases about 90%. The lower limit on the CDBI₅₀ of the first ethylene interpolymer may be about 70%, in other cases about 75% and in still other cases about 80%.

The upper limit on the M_(w)/M_(n) (the SEC determined weight average molecular weight (M_(w)) divided by the number average molecular weight (M_(n))) of the first ethylene interpolymer may be about 2.8, in other cases about 2.5 and in still other cases about 2.2. The lower limit on the M_(w)/M_(n) the first ethylene interpolymer may be about 1.7, in other cases about 1.8 and in still other cases about 1.9.

The first ethylene interpolymer, produced with the bridged metallocene catalyst formulation, contains long chain branching characterized by the LCBF disclosed herein. The upper limit on the LCBF of the first ethylene interpolymer may be about 0.5, in other cases about 0.4 and in still other cases about 0.3 (dimensionless). The lower limit on the LCBF of the first ethylene interpolymer may be about 0.001, in other cases about 0.0015 and in still other cases about 0.002 (dimensionless).

The first ethylene interpolymer contained catalyst residues that reflect the chemical composition of the first homogeneous catalyst formulation. Those skilled in the art will understand that catalyst residues are typically quantified by the parts per million of metal in the first ethylene interpolymer, where metal originates from the metal in catalyst component A (Formula (I)); hereinafter this metal will be referred to “metal A”. As recited earlier in this disclosure, non-limiting examples of metal A include Group 4 metals, titanium, zirconium and hafnium. The upper limit on the ppm of metal A in the first ethylene interpolymer may be about 3.0 ppm, in other cases about 2.0 ppm and in still other cases about 1.5 ppm. The lower limit on the ppm of metal A in the first ethylene interpolymer may be about 0.03 ppm, in other cases about 0.09 ppm and in still other cases about 0.15 ppm.

The amount of hydrogen added to R1 can vary over a wide range allowing the continuous solution process to produce first ethylene interpolymers that differ greatly in melt index, hereinafter I₂ ¹ (melt index was measured at 190° C. using a 2.16 kg load following the procedures outlined in ASTM D1238). This was accomplished by adjusting the hydrogen flow rate in stream 4 (as shown in FIG. 2). The quantity of hydrogen added to R1 was expressed as the parts-per-million (ppm) of hydrogen in R1 relative to the total mass in reactor R1; hereinafter H₂ ^(R1) (ppm). In some cases H₂ ^(R1) (ppm) ranges from about 100 ppm to 0 ppm, in other cases from about 50 ppm to 0 ppm, in alternative cases from about 20 ppm to 0 ppm and in still other cases from about 2 ppm to 0 ppm. The upper limit on I₂ ¹ may be about 200 dg/min, in some cases about 100 dg/min; in other cases about 50 dg/min, and; in still other cases about 1 dg/min. The lower limit on I₂ ¹ may be about 0.01 dg/min, in some cases about 0.05 dg/min; in other cases about 0.1 dg/min, and; in still other cases about 0.5 dg/min.

The upper limit on the weight percent (wt %) of the first ethylene interpolymer in the ethylene interpolymer product may be about 60 wt %, in other cases about 55 wt % and in still other cases about 50 wt %. The lower limit on the wt % of the first ethylene interpolymer in the ethylene interpolymer product may be about 5 wt %; in other cases about 8 wt % and in still other cases about 10 wt %.

Second Ethylene Interpolymer

The second ethylene interpolymer was synthesized using the second homogeneous catalyst formulation. One embodiment of the second homogeneous catalyst formulation was an unbridged single site catalyst formulation. Referring to the embodiments shown in FIG. 2, if optional α-olefin was not added to reactor 12 a (R2) either through fresh α-olefin stream 8 or carried over from reactor 11 a (R1) in stream 11 e (in series mode), then the ethylene interpolymer produced in reactor 12 a (R2) was an ethylene homopolymer. If an optional α-olefin is present in R2, the following weight ratio was one parameter to control the density of the second ethylene interpolymer produced in R2: ((α-olefin)/(ethylene))^(R2). The upper limit on ((α-olefin)/(ethylene))^(R2) may be about 3; in other cases about 2 and in still other cases about 1. The lower limit on ((α-olefin)/(ethylene))^(R2) may be 0; in other cases about 0.25 and in still other cases about 0.5. Hereinafter, the symbol “σ²” refers to the density of the ethylene interpolymer produced in R2. The upper limit on σ² may be about 0.975 g/cm³; in some cases about 0.965 g/cm³ and; in other cases about 0.955 g/cm³. The lower limit on σ² may be about 0.855 g/cm³, in some cases about 0.865 g/cm³, and; in other cases about 0.875 g/cm³.

The upper limit on the CDBI₅₀ of the second ethylene interpolymer (that contains an α-olefin) may be about 98%, in other cases about 95% and in still other cases about 90%. The lower limit on the CDBI₅₀ of the second ethylene interpolymer may be about 70%, in other cases about 75% and in still other cases about 80%. If an α-olefin is not added to the continuous solution polymerization process the second ethylene interpolymer was an ethylene homopolymer. In the case of a homopolymer, which does not contain α-olefin, one can still measure a CDBI₅₀ using TREF. In the case of a homopolymer, the upper limit on the CDBI₅₀ of the second ethylene interpolymer may be about 98%, in other cases about 96% and in still other cases about 95%, and; the lower limit on the CDBI₅₀ may be about 88%, in other cases about 89% and in still other cases about 90%. It is well known to those skilled in the art that as the α-olefin content in the second ethylene interpolymer approaches zero, there is a smooth transition between the recited CDBI₅₀ limits for the second ethylene interpolymers (that contain an α-olefin) and the recited CDBI₅₀ limits for the second ethylene interpolymers that are ethylene homopolymers.

The upper limit on the M_(w)/M_(n) of the second ethylene interpolymer may be about 2.8, in other cases about 2.5 and in still other cases about 2.2. The lower limit on the M_(w)/M_(n) of the second ethylene interpolymer may be about 1.7, in other cases about 1.8 and in still other cases about 1.9.

The second ethylene interpolymer produced with the second homogeneous catalyst formulation was characterized by an undetectable level of long chain branching, i.e. LCBF of <0.001 (dimensionless).

The second ethylene interpolymer contains catalyst residues that reflect the chemical composition of the second homogeneous catalyst formulation. More specifically, the second ethylene interpolymer contains “a metal C” that originates from the bulky ligand-metal complex, i.e. component C (Formula (II)). Non-limiting examples of metal C include Group 4 metals, titanium, zirconium and hafnium. The upper limit on the ppm of metal C in the second ethylene interpolymer may be about 3.0 ppm, in other cases about 2.0 ppm and in still other cases about 1.5 ppm. The lower limit on the ppm of metal C in the second ethylene interpolymer may be about 0.03 ppm, in other cases about 0.09 ppm and in still other cases about 0.15 ppm.

Referring to the embodiments shown in FIG. 2, the amount of hydrogen added to R2 can vary over a wide range which allows the continuous solution process to produce second ethylene interpolymers that differ greatly in melt index, hereinafter I₂ ². This is accomplished by adjusting the hydrogen flow rate in stream 9. The quantity of hydrogen added was expressed as the parts-per-million (ppm) of hydrogen in R2 relative to the total mass in reactor R2; hereinafter H₂ ^(R2) (ppm). In some cases H₂ ^(R2) (ppm) ranges from about 100 ppm to 0 ppm, in some cases from about 50 ppm to 0 ppm, in other cases from about 20 to 0 and in still other cases from about 2 ppm to 0 ppm. The upper limit on I₂ ² may be about 1000 dg/min; in some cases about 750 dg/min; in other cases about 500 dg/min, and; in still other cases about 200 dg/min. The lower limit on I₂ ² may be about 0.3 dg/min, in some cases about 0.4 dg/min, in other cases about 0.5 dg/min, and; in still other cases about 0.6 dg/min.

The upper limit on the weight percent (wt %) of the second ethylene interpolymer in the ethylene interpolymer product may be about 95 wt %, in other cases about 92 wt % and in still other cases about 90 wt %. The lower limit on the wt % of the second ethylene interpolymer in the ethylene interpolymer product may be about 20 wt %; in other cases about 30 wt % and in still other cases about 40 wt %.

Third Ethylene Interpolymer

Optionally, the disclosed ethylene interpolymer products contain a third ethylene interpolymer. Referring to the embodiments shown in FIG. 2 a third ethylene interpolymer was not produced in reactor 17 (R3) if catalyst deactivator A was added upstream of reactor 17 via catalyst deactivator tank 18A. If catalyst deactivator A was not added and optional α-olefin was not added to reactor 17 either through fresh α-olefin stream 15 or carried over from reactor 12 a (R2) in stream 12 c (series mode) or stream 12 d (parallel mode) then the ethylene interpolymer produced in reactor 17 was an ethylene homopolymer. If catalyst deactivator A was not added and optional α-olefin was present in R3, the following weight ratio was one parameter that determined the density of the third ethylene interpolymer: ((α-olefin)/(ethylene))^(R3). The upper limit on ((α-olefin)/(ethylene))^(R3) may be about 3; in other cases about 2 and in still other cases about 1. The lower limit on ((α-olefin)/(ethylene))^(R3) may be 0; in other cases about 0.25 and in still other cases about 0.5. Hereinafter, the symbol “σ³” refers to the density of the ethylene interpolymer produced in R3. The upper limit on σ³ may be about 0.975 g/cm³; in some cases about 0.965 g/cm³ and; in other cases about 0.955 g/cm³. Depending on the catalyst formulations used in R3, the lower limit on σ³ may be about 0.855 g/cm³, in some cases about 0.865 g/cm³, and; in other cases about 0.875 g/cm³.

Optionally, one or more of the following homogeneous or heterogeneous catalyst formulations may be injected into R3: the first homogeneous catalyst formulation, the second homogeneous catalyst formulation, the fifth homogeneous catalyst formulation or the heterogeneous catalyst formulation. One embodiment of the first homogeneous catalyst formulation was the bridged metallocene catalyst formulation containing component A (Formula (I)), in this case the third ethylene interpolymer contains metal A. The upper limit on the ppm of metal A in the third ethylene interpolymer may be about 3.0 ppm, in other cases about 2.0 ppm and in still other cases about 1.5 ppm. The lower limit on the ppm of metal A in the third ethylene interpolymer may be about 0.03 ppm, in other cases about 0.09 ppm and in still other cases about 0.15 ppm. One embodiment of the second homogeneous catalyst formulation was the unbridged single site catalyst formulation containing component C (Formula (II)), in this case the third ethylene interpolymer contains metal C. The upper limit on the ppm of metal A in the third ethylene interpolymer may be about 3.0 ppm, in other cases about 2.0 ppm and in still other cases about 1.5 ppm. The lower limit on the ppm of metal A in the third ethylene interpolymer may be about 0.03 ppm, in other cases about 0.09 ppm and in still other cases about 0.15 ppm. Embodiments of the heterogeneous catalyst formulation include an in-line Ziegler-Natta catalyst formulation or a batch Ziegler-Natta catalyst formulation; in this case the third ethylene interpolymer contains metal Z that originates from the transition metal compound (component (vii)) used to fabricate the Ziegler-Natta catalyst formulation. The upper limit on the ppm of metal Z in the third ethylene interpolymer may be about 12 ppm, in other cases about 10 ppm and in still other cases about 8 ppm. The lower limit on the ppm of metal Z in the third ethylene interpolymer may be about 0.5 ppm, in other cases about 1 ppm and in still other cases about 3 ppm. If the fifth homogeneous catalyst formulation is employed, comprising a bulky ligand-metal complex that is not a member of the genera defined by Formulas (I) or (II) the third ethylene interpolymer contains metal D. The upper limit on the ppm of metal D in the third ethylene interpolymer may be about 3.0 ppm, in other cases about 2.0 ppm and in still other cases about 1.5 ppm. The lower limit on the ppm of metal D in the third ethylene interpolymer may be about 0.03 ppm, in other cases about 0.09 ppm and in still other cases about 0.15 ppm.

The upper limit on the CDBI₅₀ of the optional third ethylene interpolymer (containing an α-olefin) may be about 98%, in other cases about 95% and in still other cases about 90%. The lower limit on the CDBI₅₀ of the optional third ethylene interpolymer may be about 35%, in other cases about 40% and in still other cases about 45%.

The upper limit on the M_(w)/M_(n) of the optional third ethylene interpolymer may be about 5.0, in other cases about 4.8 and in still other cases about 4.5. The lower limit on the M_(w)/M_(n) of the optional third ethylene interpolymer may be about 1.7, in other cases about 1.8 and in still other cases about 1.9.

Referring to the embodiments shown in FIG. 2, optional hydrogen may be added to the tubular reactor (R3) via stream 16. The amount of hydrogen added to R3 may vary over a wide range. Adjusting the amount of hydrogen in R3, hereinafter H₂ ^(R3) (ppm), allows the continuous solution process to produce optional third ethylene interpolymers that differ widely in melt index, hereinafter I₂ ³. The amount of optional hydrogen added to R3 ranges from about 50 ppm to 0 ppm, in some cases from about 25 ppm to 0 ppm, in other cases from about 10 to 0 and in still other cases from about 2 ppm to 0 ppm. The upper limit on I₂ ³ may be about 2000 dg/min; in some cases about 1500 dg/min; in other cases about 1000 dg/min, and; in still other cases about 500 dg/min. The lower limit on I₂ ³ may be about 0.5 dg/min, in some cases about 0.6 dg/min, in other cases about 0.7 dg/min, and; in still other cases about 0.8 dg/min.

The upper limit on the weight percent (wt %) of the optional third ethylene interpolymer in the ethylene interpolymer product may be about 30 wt %, in other cases about 25 wt % and in still other cases about 20 wt %. The lower limit on the wt % of the optional third ethylene interpolymer in the ethylene interpolymer product may be 0 wt %; in other cases about 5 wt % and in still other cases about 10 wt %.

Ethylene Interpolymer Product

The upper limit on the density of the ethylene interpolymer product (ρ^(f)) may be about 0.975 g/cm³; in some cases about 0.965 g/cm³ and; in other cases about 0.955 g/cm³. The lower limit on the density of the ethylene interpolymer product may be about 0.855 g/cm³, in some cases about 0.865 g/cm³, and; in other cases about 0.875 g/cm³.

The upper limit on the CDBI₅₀ of the ethylene interpolymer product may be about 97%, in other cases about 90% and in still other cases about 85%. An ethylene interpolymer product with a CDBI₅₀ of 97% may result if an α-olefin is not added to the continuous solution polymerization process; in this case, the ethylene interpolymer product is an ethylene homopolymer. The lower limit on the CDBI₅₀ of an ethylene interpolymer product may be about 1%, in other cases about 2% and in still other cases about 3%.

The upper limit on the M_(w)/M_(n) of the ethylene interpolymer product may be about 25, in other cases about 15 and in still other cases about 9. The lower limit on the M_(w)/M_(n) of the ethylene interpolymer product may be 1.7, in other cases about 1.8 and in still other cases about 1.9.

The catalyst residues in the ethylene interpolymer product reflect the chemical compositions of: the first homogeneous catalyst formulation employed in R1; the second homogeneous catalyst formulation employed in R2, and; optionally one or more catalyst formulations employed in R3. Catalyst residues were quantified by measuring the parts per million of catalytic metal in the ethylene interpolymer products using Neutron Activation Analysis (N.A.A.). As shown in Table 5, the ethylene interpolymer product Example 52 contained 0.624 ppm hafnium and 0.208 ppm titanium. As shown in Table 4A, Example 52 was produced with reactors 1 and 2 operating in parallel mode, a hafnium (Hf) containing bridged metallocene catalyst formulation was injected into reactor 1 and a titanium (Ti) containing unbridged single site catalyst formulation was injected into reactor 2 (catalysts were not injected into reactor 3). Further, in Example 52, Hf originated from CpF-2 (the [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂] species of component A (Formula (I)) and Ti originated from PIC-1 (the [Cp[(isopropyl)₃PN]TiCl2] species of component C (Formula (II)). Example 52 had a residual catalyst Hf/Ti ratio of 3.0 (0.624 ppm Hf/0.208 ppm Ti).

As shown in Table 5, the Comparatives contained undetectable levels of hafnium (0.0 ppm hafnium) and about 0.303 ppm of titanium, i.e. a residual catalyst Hf/Ti ratio of 0.0. As shown in Table 4A, Comparative 60 was produced with reactors 1 and 2 operating in series mode, an unbridged single site catalyst formulation (Ti containing) was injected into both reactor 1 and reactor 2 (catalysts were not injected into reactor 3). In Comparative 60 the Ti source was: PIC-2, the cyclopentadienyl tri(isopropyl) phosphinimine titanium dichloride species [Cp[(i-prop)₃PN]TiCl₂] of component C (Formula (II))).

As shown in Table 5, ethylene interpolymer product Example 51 contained 0.530 ppm Hf and 0.127 ppm Ti and the residual catalyst Hf/Ti ratio was 4.17. As shown in Table 4A, Example 51 was produced with reactors 1 and 2 operating in series mode, a Hf containing (CpF-2) bridged metallocene catalyst formulation was injected into reactor 1 and a Ti containing (PIC-1) unbridged single site catalyst formulation was injected into reactor 2 (catalysts were not injected into reactor 3).

Comparative 67 contained 0.0 ppm of Hf and about 0.303 ppm Ti and the residual catalyst Hf/Ti ratio was 0.0. Comparative 67 was produced using the unbridged single site catalyst formulation in both reactors 1 and 2. Comparative 67 was a commercially available solution process ethylene/1-octene polymer produced by NOVA Chemicals Company (Calgary, Alberta, Canada) coded SURPASS® FPs117-C.

The upper limit on the ppm of metal A in the ethylene interpolymer product was determined by maximizing the weight fraction (i.e. 0.60) of the first ethylene interpolymer, minimizing the weight fraction (i.e. 0.20) of the second ethylene interpolymer and the remaining weight fraction (i.e. 0.20) was the third ethylene interpolymer produced with catalytic metal A, i.e. the bridged metallocene catalyst formulation. Specifically, the upper limit on the ppm of metal A in the ethylene interpolymer product was 2.4 ppm: i.e. ((0.6×3 ppm)+(0.2×3 ppm)); where 3 ppm is the upper limit on the ppm of metal A in the first and third ethylene interpolymers. In other cases, the upper limit on the ppm of metal A in the ethylene interpolymer product was 2 ppm and in still other cases 1.5 ppm. The lower limit on the ppm of metal A in the ethylene interpolymer product was determined by minimizing the weight fraction (i.e. 0.05) of the first ethylene interpolymer and maximizing the weight fraction (i.e. 0.95) of the second ethylene interpolymer. Specifically, the lower limit on the ppm of metal A in the ethylene interpolymer product was 0.0015 ppm: i.e. (0.05×0.03 ppm), where 0.03 ppm was the lower limit of metal A in the first ethylene interpolymer. In other cases, the lower limit on the ppm of metal A in the ethylene interpolymer product was 0.0025 ppm and in still other cases 0.0035 ppm.

The upper limit on the ppm of metal C in the ethylene interpolymer product was determined by maximizing the weight fraction (i.e. 0.95) of the second ethylene interpolymer, i.e. 2.9 ppm (0.95×3 ppm), where 3 ppm was the upper limit on the ppm of metal C in the second ethylene interpolymer. In other cases, the upper limit on the amount of metal C in the ethylene interpolymer product was 1.9 ppm and in still other cases 1.4 ppm. The lower limit on the ppm of metal C in the ethylene interpolymer product was determined by minimizing the weight fraction (i.e. 0.20) of the second ethylene interpolymer, i.e. 0.006 ppm (0.20×0.03 ppm), where 0.03 ppm was the lower limit on the ppm of metal C in the second ethylene interpolymer. In other cases, the lower limit on the ppm of metal C in the ethylene interpolymer product was 0.02 ppm and in still other cases 0.03 ppm.

The upper limit on the ppm of metal D (originating from the fifth homogeneous catalyst formulation) in the ethylene interpolymer product was determined by maximizing the weight fraction (i.e. 0.30) of the third ethylene interpolymer, i.e. 0.9 ppm (0.3×3 ppm), where 3 ppm is the upper limit on the ppm of metal D in the third ethylene interpolymer. In other cases, the upper limit on the ppm of metal D in the ethylene interpolymer product was 0.7 ppm and in still other cases 0.5 ppm. The lower limit on the ppm of metal D in the ethylene interpolymer product was determined by minimizing the weight fraction (i.e. 0.0) of the third ethylene interpolymer, i.e. 0.0 ppm. In other cases when the ethylene interpolymer product contains a small fraction of the third ethylene interpolymer the lower limit on the ppm of metal D in the ethylene interpolymer product may be 0.0015 ppm or 0.003 ppm, i.e. 5 and 10% of the third ethylene interpolymer, respectively.

The upper limit on the ppm of metal Z in the ethylene interpolymer product was determined by maximizing the weight fraction (i.e. 0.30) of the third ethylene interpolymer, i.e. 3.6 ppm (0.30×12 ppm), where 12 ppm was the upper limit on the ppm of metal Z in the third ethylene interpolymer. In other cases, the upper limit on amount of metal Z in the ethylene interpolymer product was 3 ppm and in still other cases 2.4 ppm. The lower limit on the ppm of metal Z in the ethylene interpolymer product was determined by minimizing the weight fraction (i.e. 0.0) of the third ethylene interpolymer, i.e. 0.0 ppm. In other cases where the ethylene interpolymer product contains a small fraction of the third ethylene interpolymer the lower limit on ppm of metal Z in the ethylene interpolymer product may be 0.025 ppm and in other cases 0.05 ppm, i.e. 5 and 10% of the third ethylene interpolymer, respectively.

The hafnium to titanium ratio (Hf/Ti) in the ethylene interpolymer product may range from 400 to 0.0005, as determined by Neutron Activation Analysis. A Hf/Ti ratio of 400 may result in the case of an ethylene interpolymer product containing 80 weight % of the a first and a third ethylene interpolymer containing 3 ppm of Hf (upper limit) and 20 weight % of a second ethylene interpolymer containing 0.03 ppm of Ti (lower limit). A Hf/Ti ratio of 0.0005 may result in the case of an ethylene interpolymer product containing 5 weight % of a first ethylene interpolymer containing 0.03 ppm of Hf (lower limit) and 95 weight % of a second ethylene interpolymer containing 3 ppm of Ti (upper limit).

The upper limit on the total amount of catalytic metal (metal A and metal C; and optionally metals Z and D) in the ethylene interpolymer product may be 6 ppm, in other cases 5 ppm and in still other cases 4 ppm. The lower limit on the total amount of catalytic metal in the ethylene interpolymer product may be 0.03 ppm, in other cases 0.09 ppm and in still other cases 0.15 ppm.

Embodiments of the ethylene interpolymer products disclosed herein have lower catalyst residues relative the polyethylene polymers described in U.S. Pat. No. 6,277,931. Higher catalyst residues in U.S. Pat. No. 6,277,931 increase the complexity of the continuous solution polymerization process; an example of increased complexity includes additional purification steps to remove catalyst residues from the polymer. In contrast, in the present disclosure, catalyst residues are not removed.

The upper limit on melt index of the ethylene interpolymer product may be about 500 dg/min, in some cases about 400 dg/min; in other cases about 300 dg/min, and; in still other cases about 200 dg/min. The lower limit on the melt index of the ethylene interpolymer product may be about 0.3 dg/min, in some cases about 0.4 dg/min; in other cases about 0.5 dg/min, and; in still other cases about 0.6 dg/min.

Catalyst Deactivation

In the continuous polymerization processes described in this disclosure, polymerization is terminated by adding a catalyst deactivator. Embodiments in FIG. 2 show catalyst deactivation occurring either: (a) upstream of the tubular reactor by adding a catalyst deactivator A from catalyst deactivator tank 18A, or; (b) downstream of the tubular reactor by adding a catalyst deactivator B from catalyst deactivator tank 18B. Catalyst deactivator tanks 18A and 18B may contain neat (100%) catalyst deactivator, a solution of catalyst deactivator in a solvent, or a slurry of catalyst deactivator in a solvent. The chemical composition of catalyst deactivator A and B may be the same, or different. Non-limiting examples of suitable solvents include linear or branched C₅ to C₁₂ alkanes. In this disclosure, how the catalyst deactivator is added is not particularly important. Once added, the catalyst deactivator substantially stops the polymerization reaction by changing active catalyst species to inactive forms. Suitable deactivators are well known in the art, non-limiting examples include: amines (e.g. U.S. Pat. No. 4,803,259 to Zboril et al.); alkali or alkaline earth metal salts of carboxylic acid (e.g. U.S. Pat. No. 4,105,609 to Machan et al.); water (e.g. U.S. Pat. No. 4,731,438 to Bernier et al.); hydrotalcites, alcohols and carboxylic acids (e.g. U.S. Pat. No. 4,379,882 to Miyata); or a combination thereof (U.S. Pat. No. 6,180,730 to Sibtain et al.). In this disclosure the quantify of catalyst deactivator added was determined by the following catalyst deactivator molar ratio: 0.3≤(catalyst deactivator)/((total catalytic metal)+(alkyl aluminum co-catalyst)+(aluminum alkyl))≤2.0; where the catalytic metal is the total moles of (metal A+metal C+any optional catalytic metals added the third reactor). The upper limit on the catalyst deactivator molar ratio may be about 2, in some cases about 1.5 and in other cases about 0.75. The lower limit on the catalyst deactivator molar ratio may be about 0.3, in some cases about 0.35 and in still other cases about 0.4. In general, the catalyst deactivator is added in a minimal amount such that the catalyst is deactivated and the polymerization reaction is quenched.

Solution Passivation

If a heterogeneous catalyst formulation is employed in the third reactor, prior to entering the first V/L separator, a passivator or acid scavenger is added to deactivated solution A or B to form a passivated solution, i.e. passivated solution stream 23 as shown in FIG. 2. Passivator tank 22 may contain neat (100%) passivator, a solution of passivator in a solvent, or a slurry of passivator in a solvent. Non-limiting examples of suitable solvents include linear or branched C₅ to C₁₂ alkanes. In this disclosure, how the passivator is added is not particularly important. Suitable passivators are well known in the art, non-limiting examples include alkali or alkaline earth metal salts of carboxylic acids or hydrotalcites. The quantity of passivator added can vary over a wide range. The quantity of passivator added was determined by the total moles of chloride compounds added to the solution process, i.e. the chloride compound “compound (vi)” plus the metal compound “compound (vii)” that was used to manufacture the heterogeneous catalyst formulation. The upper limit on the (passivator)/(total chlorides) molar ratio may be 15, in some cases 13 and in other cases 11. The lower limit on the (passivator)/(total chlorides) molar ratio may be about 5, in some cases about 7 and in still other cases about 9. In general, the passivator is added in the minimal amount to substantially passivate the deactivated solution.

Flexible Manufactured Articles

The ethylene interpolymer products disclosed herein may be converted into flexible manufactured articles such as monolayer or multilayer films. Non-limiting examples of processes to prepare such films include blown film processes, double bubble processes, triple bubble processes, cast film processes, tenter frame processes and machine direction orientation (MDO) processes.

In the blown film extrusion process an extruder heats, melts, mixes and conveys a thermoplastic, or a thermoplastic blend. Once molten, the thermoplastic is forced through an annular die to produce a thermoplastic tube. In the case of co-extrusion, multiple extruders are employed to produce a multilayer thermoplastic tube. The temperature of the extrusion process is primarily determined by the thermoplastic or thermoplastic blend being processed, for example the melting temperature or glass transition temperature of the thermoplastic and the desired viscosity of the melt. In the case of polyolefins, typical extrusion temperatures are from 330° F. to 550° F. (166° C. to 288° C.). Upon exit from the annular die, the thermoplastic tube is inflated with air, cooled, solidified and pulled through a pair of nip rollers. Due to air inflation, the tube increases in diameter forming a bubble of desired size. Due to the pulling action of the nip rollers the bubble is stretched in the machine direction. Thus, the bubble is stretched in two directions: the transverse direction (TD) where the inflating air increases the diameter of the bubble; and the machine direction (MD) where the nip rollers stretch the bubble. As a result, the physical properties of blown films are typically anisotropic, i.e. the physical properties differ in the MD and TD directions; for example, film tear strength and tensile properties typically differ in the MD and TD. In some prior art documents, the terms “cross direction” or “CD” is used; these terms are equivalent to the terms “transverse direction” or “TD” used in this disclosure. In the blown film process, air is also blown on the external bubble circumference to cool the thermoplastic as it exits the annular die. The final width of the film is determined by controlling the inflating air or the internal bubble pressure; in other words, increasing or decreasing bubble diameter. Film thickness is controlled primarily by increasing or decreasing the speed of the nip rollers to control the draw-down rate. After exiting the nip rollers, the bubble or tube is collapsed and may be slit in the machine direction thus creating sheeting. Each sheet may be wound into a roll of film. Each roll may be further slit to create film of the desired width. Each roll of film is further processed into a variety of consumer products as described below.

The cast film process is similar in that a single or multiple extruder(s) may be used; however the various thermoplastic materials are metered into a flat die and extruded into a monolayer or multilayer sheet, rather than a tube. In the cast film process the extruded sheet is solidified on a chill roll.

In the double bubble process a first blown film bubble is formed and cooled, then the first bubble is heated and re-inflated forming a second blown film bubble, which is subsequently cooled. The ethylene interpolymer products, disclosed herein, are also suitable for the triple bubble blown process. Additional film converting processes, suitable for the disclosed ethylene interpolymer products, include processes that involve a Machine Direction Orientation (MDO) step; for example, blowing a film or casting a film, quenching the film and then subjecting the film tube or film sheet to a MDO process at any stretch ratio. Additionally, the ethylene interpolymer product films disclosed herein are suitable for use in tenter frame processes as well as other processes that introduce biaxial orientation.

Depending on the end-use application, the disclosed ethylene interpolymer products may be converted into films that span a wide range of thicknesses. Non-limiting examples include, food packaging films where thicknesses may range from about 0.5 mil (13 μm) to about 4 mil (102 μm), and; in heavy duty sack applications film thickness may range from about 2 mil (51 μm) to about 10 mil (254 μm).

The monolayer, in monolayer films, may contain more than one ethylene interpolymer product and/or one or more additional polymer; non-limiting examples of additional polymers include ethylene polymers and propylene polymers. The lower limit on the weight percent of the ethylene interpolymer product in a monolayer film may be about 3 wt %, in other cases about 10 wt % and in still other cases about 30 wt %. The upper limit on the weight percent of the ethylene interpolymer product in the monolayer film may be 100 wt %, in other cases about 90 wt % and in still other cases about 70 wt %.

The ethylene interpolymer products disclosed herein may also be used in one or more layers of a multilayer film; non-limiting examples of multilayer films include three, five, seven, nine, eleven or more layers. The disclosed ethylene interpolymer products are also suitable for use in processes that employ micro-layering dies and/or feedblocks, such processes can produce films having many layers, non-limiting examples include from 10 to 10,000 layers.

The thickness of a specific layer (containing the ethylene interpolymer product) within a multilayer film may be about 5%, in other cases about 15% and in still other cases about 30% of the total multilayer film thickness. In other embodiments, the thickness of a specific layer (containing the ethylene interpolymer product) within a multilayer film may be about 95%, in other cases about 80% and in still other cases about 65% of the total multilayer film thickness. Each individual layer of a multilayer film may contain more than one ethylene interpolymer product and/or additional thermoplastics.

Additional embodiments include laminations and coatings, wherein mono or multilayer films containing the disclosed ethylene interpolymer products are extrusion laminated or adhesively laminated or extrusion coated. In extrusion lamination or adhesive lamination, two or more substrates are bonded together with a thermoplastic or an adhesive, respectively. In extrusion coating, a thermoplastic is applied to the surface of a substrate. These processes are well known to those experienced in the art. Frequently, adhesive lamination or extrusion lamination are used to bond dissimilar materials, non-limiting examples include the bonding of a paper web to a thermoplastic web, or the bonding of an aluminum foil containing web to a thermoplastic web, or the bonding of two thermoplastic webs that are chemically incompatible, e.g. the bonding of an ethylene interpolymer product containing web to a polyester or polyamide web. Prior to lamination, the web containing the disclosed ethylene interpolymer product(s) may be monolayer or multilayer. Prior to lamination the individual webs may be surface treated to improve the bonding, a non-limiting example of a surface treatment is corona treating. A primary web or film may be laminated on its upper surface, its lower surface, or both its upper and lower surfaces with a secondary web. A secondary web and a tertiary web could be laminated to the primary web; wherein the secondary and tertiary webs differ in chemical composition. As non-limiting examples, secondary or tertiary webs may include; polyamide, polyester and polypropylene, or webs containing barrier resin layers such as EVOH. Such webs may also contain a vapor deposited barrier layer; for example a thin silicon oxide (SiO_(x)) or aluminum oxide (AlO_(x)) layer. Multilayer webs (or films) may contain three, five, seven, nine, eleven or more layers.

The ethylene interpolymer products disclosed herein can be used in a wide range of manufactured articles comprising one or more films (monolayer or multilayer). Non-limiting examples of such manufactured articles include: food packaging films (fresh and frozen foods, liquids and granular foods), stand-up pouches, retortable packaging and bag-in-box packaging; barrier films (oxygen, moisture, aroma, oil, etc.) and modified atmosphere packaging; light and heavy duty shrink films and wraps, collation shrink film, pallet shrink film, shrink bags, shrink bundling and shrink shrouds; light and heavy duty stretch films, hand stretch wrap, machine stretch wrap and stretch hood films; high clarity films; heavy-duty sacks; household wrap, overwrap films and sandwich bags; industrial and institutional films, trash bags, can liners, magazine overwrap, newspaper bags, mail bags, sacks and envelopes, bubble wrap, carpet film, furniture bags, garment bags, coin bags, auto panel films; medical applications such as gowns, draping and surgical garb; construction films and sheeting, asphalt films, insulation bags, masking film, landscaping film and bags; geomembrane liners for municipal waste disposal and mining applications; batch inclusion bags; agricultural films, mulch film and green house films; in-store packaging, self-service bags, boutique bags, grocery bags, carry-out sacks and t-shirt bags; oriented films, machine direction oriented (MDO) films, biaxially oriented films and functional film layers in oriented polypropylene (OPP) films, e.g. sealant and/or toughness layers. Additional manufactured articles comprising one or more films containing at least one ethylene interpolymer product include laminates and/or multilayer films; sealants and tie layers in multilayer films and composites; laminations with paper; aluminum foil laminates or laminates containing vacuum deposited aluminum; polyamide laminates; polyester laminates; extrusion coated laminates, and; hot-melt adhesive formulations. The manufactured articles summarized in this paragraph contain at least one film (monolayer or multilayer) comprising at least one embodiment of the disclosed ethylene interpolymer products.

Desired film physical properties (monolayer or multilayer) typically depend on the application of interest. Non-limiting examples of desirable film properties include: optical properties (gloss, haze and clarity), dart impact, Elmendorf tear, modulus (1% and 2% secant modulus), tensile properties (yield strength, break strength, elongation at break, toughness, etc.), heat sealing properties (heat seal initiation temperature, SIT, and hot tack). Specific hot tack and heat sealing properties are desired in high speed vertical and horizontal form-fill-seal processes that load and seal a commercial product (liquid, solid, paste, part, etc.) inside a pouch-like package.

In addition to desired film physical properties, it is desired that the disclosed ethylene interpolymer products are easy to process on film lines. Those skilled in the art frequently use the term “processability” to differentiate polymers with improved processability, relative to polymers with inferior processability. A commonly used measure to quantify processability is extrusion pressure; more specifically, a polymer with improved processability has a lower extrusion pressure (on a blown film or a cast film extrusion line) relative to a polymer with inferior processability.

The films used in the manufactured articles described in this section may optionally include, depending on its intended use, additives and adjuvants. Non-limiting examples of additives and adjuvants include, anti-blocking agents, antioxidants, heat stabilizers, slip agents, processing aids, anti-static additives, colorants, dyes, filler materials, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleating agents and combinations thereof.

Rigid Manufactured Articles

The processes disclosed herein are also capable of making ethylene interpolymer products that have a useful combination of desirable physical properties for use in rigid manufactured articles. Non-limiting examples of rigid articles include: deli containers, margarine tubs, drink cups and produce trays; household and industrial containers, cups, bottles, pails, crates, tanks, drums, bumpers, lids, industrial bulk containers, industrial vessels, material handling containers, bottle cap liners, bottle caps, living hinge closures; toys, playground equipment, recreational equipment, boats, marine and safety equipment; wire and cable applications such as power cables, communication cables and conduits; flexible tubing and hoses; pipe applications including both pressure pipe and non-pressure pipe markets, e.g. natural gas distribution, water mains, interior plumbing, storm sewer, sanitary sewer, corrugated pipes and conduit; foamed articles manufactured from foamed sheet or bun foam; military packaging (equipment and ready meals); personal care packaging, diapers and sanitary products; cosmetic, pharmaceutical and medical packaging, and; truck bed liners, pallets and automotive dunnage. The rigid manufactured articles summarized in this paragraph contain one or more of the ethylene interpolymer products disclosed herein or a blend of at least one of the ethylene interpolymer products disclosed herein with at least one other thermoplastic.

Such rigid manufactured articles may be fabricated using the following non-limiting processes: injection molding, compression molding, blow molding, rotomolding, profile extrusion, pipe extrusion, sheet thermoforming and foaming processes employing chemical or physical blowing agents.

The desired physical properties of rigid manufactured articles depend on the application of interest. Non-limiting examples of desired properties include: flexural modulus (1% and 2% secant modulus); tensile toughness; environmental stress crack resistance (ESCR); slow crack growth resistance (PENT); abrasion resistance; shore hardness; deflection temperature under load; VICAT softening point; IZOD impact strength; ARM impact resistance; Charpy impact resistance, and; color (whiteness and/or yellowness index).

The rigid manufactured articles described in this section may optionally include, depending on its intended use, additives and adjuvants. Non-limiting examples of additives and adjuvants include, antioxidants, slip agents, processing aids, anti-static additives, colorants, dyes, filler materials, heat stabilizers, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleating agents and combinations thereof.

Testing Methods

Prior to testing, each specimen was conditioned for at least 24 hours at 23±2° C. and 50±10% relative humidity and subsequent testing was conducted at 23±2° C. and 50±10% relative humidity. Herein, the term “ASTM conditions” refers to a laboratory that is maintained at 23±2° C. and 50±10% relative humidity; and specimens to be tested were conditioned for at least 24 hours in this laboratory prior to testing. ASTM refers to the American Society for Testing and Materials.

Density

ylene interpolymer product densities were determined using ASTM D792-13 (Nov. 1, 2013).

Melt Index

Ethylene interpolymer product melt index was determined using ASTM D1238 (Aug. 1, 2013). Melt indexes, I₂, I₆, I₁₀ and I₂₁ were measured at 190° C., using weights of 2.16 kg, 6.48 kg, 10 kg and a 21.6 kg respectively. Herein, the term “stress exponent” or its acronym “S.Ex.”, is defined by the following relationship: S.Ex.=log(I ₆ /I ₂)/log(6480/2160) wherein I₆ and I₂ are the melt flow rates measured at 190° C. using 6.48 kg and 2.16 kg loads, respectively.

Conventional Size Exclusion Chromatography (SEC)

Ethylene interpolymer product samples (polymer) solutions (1 to 3 mg/mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel for 4 hours at 150° C. in an oven. An antioxidant (2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture in order to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Polymer solutions were chromatographed at 140° C. on a PL 220 high-temperature chromatography unit equipped with four Shodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL/minute, with a differential refractive index (DRI) as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect GPC columns from oxidative degradation. The sample injection volume was 200 μL. The GPC columns were calibrated with narrow distribution polystyrene standards. The polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in the ASTM standard test method D6474-12 (December 2012). The GPC raw data were processed with the Cirrus GPC software, to produce molar mass averages (M_(n), M_(w), M_(z)) and molar mass distribution (e.g. Polydispersity, M_(w)/M_(n)). In the polyethylene art, a commonly used term that is equivalent to SEC is GPC, i.e. Gel Permeation Chromatography.

Triple Detection Size Exclusion Chromatography (3D-SEC)

Ethylene interpolymer product samples (polymer) solutions (1 to 3 mg/mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel for 4 hours at 150° C. in an oven. An antioxidant (2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture in order to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Sample solutions were chromatographed at 140° C. on a PL 220 high-temperature chromatography unit equipped with a differential refractive index (DRI) detector, a dual-angle light scattering detector (15 and 90 degree) and a differential viscometer. The SEC columns used were either four Shodex columns (HT803, HT804, HT805 and HT806), or four PL Mixed ALS or BLS columns. TCB was the mobile phase with a flow rate of 1.0 mL/minute, BHT was added to the mobile phase at a concentration of 250 ppm to protect SEC columns from oxidative degradation. The sample injection volume was 200 μL. The SEC raw data were processed with the Cirrus GPC software, to produce absolute molar masses and intrinsic viscosity ([η]). The term “absolute” molar mass was used to distinguish 3D-SEC determined absolute molar masses from the molar masses determined by conventional SEC. The viscosity average molar mass (M_(v)) determined by 3D-SEC was used in the calculations to determine the Long Chain Branching Factor (LCBF).

GPC-FTIR

Ethylene interpolymer product (polymer) solutions (2 to 4 mg/mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel for 4 hours at 150° C. in an oven. The antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in order to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Sample solutions were chromatographed at 140° C. on a Waters GPC 150C chromatography unit equipped with four Shodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL/minute, with a FTIR spectrometer and a heated FTIR flow through cell coupled with the chromatography unit through a heated transfer line as the detection system. BHT was added to the mobile phase at a concentration of 250 ppm to protect SEC columns from oxidative degradation. The sample injection volume was 300 μL. The raw FTIR spectra were processed with OPUS FTIR software and the polymer concentration and methyl content were calculated in real time with the Chemometric Software (PLS technique) associated with the OPUS. Then the polymer concentration and methyl content were acquired and baseline-corrected with the Cirrus GPC software. The SEC columns were calibrated with narrow distribution polystyrene standards. The polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in the ASTM standard test method D6474. The comonomer content was calculated based on the polymer concentration and methyl content predicted by the PLS technique as described in Paul J. DesLauriers, Polymer 43, pages 159-170 (2002); herein incorporated by reference.

The GPC-FTIR method measures total methyl content, which includes the methyl groups located at the ends of each macromolecular chain, i.e. methyl end groups. Thus, the raw GPC-FTIR data must be corrected by subtracting the contribution from methyl end groups. To be more clear, the raw GPC-FTIR data overestimates the amount of short chain branching (SCB) and this overestimation increases as molecular weight (M) decreases. In this disclosure, raw GPC-FTIR data was corrected using the 2-methyl correction. At a given molecular weight (M), the number of methyl end groups (N_(E)) was calculated using the following equation; N_(E)=28000/M, and N_(E) (M dependent) was subtracted from the raw GPC-FTIR data to produce the SCB/1000C (2-Methyl Corrected) GPC-FTIR data.

Composition Distribution Branching Index (CDBI)

The “Composition Distribution Branching Index”, hereinafter CDBI, of the disclosed Examples and Comparative Examples were measured using a CRYSTAF/TREF 200+ unit equipped with an IR detector, hereinafter the CTREF. The acronym “TREF” refers to Temperature Rising Elution Fractionation. The CTREF was supplied by PolymerChAR S.A. (Valencia Technology Park, Gustave Eiffel, 8, Paterna, E-46980 Valencia, Spain). The CTREF was operated in the TREF mode, which generates the chemical composition of the polymer sample as a function of elution temperature, the Co/Ho ratio (Copolymer/Homopolymer ratio) and the CDBI (the Composition Distribution Breadth Index), i.e. CDBI₅₀ and CDBI₂₅. A polymer sample (80 to 100 mg) was placed into the reactor vessel of the CTREF. The reactor vessel was filled with 35 ml of 1,2,4-trichlorobenzene (TCB) and the polymer was dissolved by heating the solution to 150° C. for 2 hours. An aliquot (1.5 mL) of the solution was then loaded into the CTREF column which was packed with stainless steel beads. The column, loaded with sample, was allowed to stabilize at 110° C. for 45 minutes. The polymer was then crystallized from solution, within the column, by dropping the temperature to 30° C. at a cooling rate of 0.09° C./minute. The column was then equilibrated for 30 minutes at 30° C. The crystallized polymer was then eluted from the column with TCB flowing through the column at 0.75 mL/minute, while the column was slowly heated from 30° C. to 120° C. at a heating rate of 0.25° C./minute. The raw CTREF data were processed using Polymer ChAR software, an Excel spreadsheet and CTREF software developed in-house. CDBI₅₀ was defined as the percent of polymer whose composition is within 50% of the median comonomer composition; CDBI₅₀ was calculated from the composition distribution cure and the normalized cumulative integral of the composition distribution curve, as described in U.S. Pat. No. 5,376,439. Those skilled in the art will understand that a calibration curve is required to convert a CTREF elution temperature to comonomer content, i.e. the amount of comonomer in the ethylene/α-olefin polymer fraction that elutes at a specific temperature. The generation of such calibration curves are described in the prior art, e.g. Wild, et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455: hereby fully incorporated by reference. CDBI₂₅ as calculated in a similar manner; CDBI₂₅ is defined as the percent of polymer whose composition is with 25% of the median comonomer composition. At the end of each sample run, the CTREF column was cleaned for 30 minutes; specifically, with the CTREF column temperature at 160° C., TCB flowed (0.5 mL/minute) through the column for 30 minutes. CTREF deconvolutions were performed to determine the amount of branching (BrF (#C6/1000C)) and density of the first ethylene interpolymer using the following equations: BrF (#C₆/1000C)=74.29-0.7598 (T^(P) _(CTREF)), where T^(P) _(CTREF) is the peak elution temperature of the first ethylene interpolymer in the CTREF chromatogram, and BrF (#C₆/1000C)=9341.8 (ρ¹)²−17766 (ρ¹)+8446.8, where ρ¹ was the density of the first ethylene interpolymer. The BrF (#C₆/1000C) and density of the second ethylene interpolymer was determined using blending rules, given the overall BrF (#C₆/1000C) and density of the ethylene interpolymer product. The BrF (#C₆/1000C) and density of the second and third ethylene interpolymer was assumed to be the same.

Neutron Activation (Elemental Analysis)

Neutron Activation Analysis, hereinafter N.A.A., was used to determine catalyst residues in ethylene interpolymer products as follows. A radiation vial (composed of ultrapure polyethylene, 7 mL internal volume) was filled with an ethylene interpolymer product sample and the sample weight was recorded. Using a pneumatic transfer system the sample was placed inside a SLOWPOKE™ nuclear reactor (Atomic Energy of Canada Limited, Ottawa, Ontario, Canada) and irradiated for 30 to 600 seconds for short half-life elements (e.g., Ti, V, Al, Mg, and Cl) or 3 to 5 hours for long half-life elements (e.g. Zr, Hf, Cr, Fe and Ni). The average thermal neutron flux within the reactor was 5×10¹¹/cm²/s. After irradiation, samples were withdrawn from the reactor and aged, allowing the radioactivity to decay; short half-life elements were aged for 300 seconds or long half-life elements were aged for several days. After aging, the gamma-ray spectrum of the sample was recorded using a germanium semiconductor gamma-ray detector (Ortec model GEM55185, Advanced Measurement Technology Inc., Oak Ridge, Tenn., USA) and a multichannel analyzer (Ortec model DSPEC Pro). The amount of each element in the sample was calculated from the gamma-ray spectrum and recorded in parts per million relative to the total weight of the ethylene interpolymer product sample. The N.A.A. system was calibrated with Specpure standards (1000 ppm solutions of the desired element (greater than 99% pure)). One mL of solutions (elements of interest) were pipetted onto a 15 mm×800 mm rectangular paper filter and air dried. The filter paper was then placed in a 1.4 mL polyethylene irradiation vial and analyzed by the N.A.A. system. Standards are used to determine the sensitivity of the N.A.A. procedure (in counts/μg).

Unsaturation

The quantity of unsaturated groups, i.e. double bonds, in an ethylene interpolymer product was determined according to ASTM D3124-98 (vinylidene unsaturation, published March 2011) and ASTM D6248-98 (vinyl and trans unsaturation, published July 2012). An ethylene interpolymer product sample was: a) first subjected to a carbon disulfide extraction to remove additives that may interfere with the analysis; b) the sample (pellet, film or granular form) was pressed into a plaque of uniform thickness (0.5 mm), and; c) the plaque was analyzed by FTIR.

Comonomer Content: Fourier Transform Infrared (FTIR) Spectroscopy

The quantity of comonomer in an ethylene interpolymer product was determine by FTIR and reported as the Short Chain Branching (SCB) content having dimensions of CH₃#/1000C (number of methyl branches per 1000 carbon atoms). This test was completed according to ASTM D6645-01 (2001), employing a compression molded polymer plaque and a Thermo-Nicolet 750 Magna-IR Spectrophotometer. The polymer plaque was prepared using a compression molding device (Wabash-Genesis Series press) according to ASTM D4703-16 (April 2016).

Dynamic Mechanical Analysis (DMA)

Oscillatory shear measurements under small strain amplitudes were carried out to obtain linear viscoelastic functions at 190° C. under N₂ atmosphere, at a strain amplitude of 10% and over a frequency range of 0.02-126 rad/s at 5 points per decade. Frequency sweep experiments were performed with a TA Instruments DHR3 stress-controlled rheometer using cone-plate geometry with a cone angle of 5°, a truncation of 137 μm and a diameter of 25 mm. In this experiment a sinusoidal strain wave was applied and the stress response was analyzed in terms of linear viscoelastic functions. The zero shear rate viscosity (θ₀) based on the DMA frequency sweep results was predicted by Ellis model (see R. B. Bird et al. “Dynamics of Polymer Liquids. Volume 1: Fluid Mechanics” Wiley-Interscience Publications (1987) p. 228) or Carreau-Yasuda model (see K. Yasuda (1979) PhD Thesis, IT Cambridge). In this disclosure, the LCBF (Long Chain Branching Factor) was determined using the DMA determined θ₀.

Creep Test

Creep measurements were performed by an Anton Paar MCR 501 rheometer at 190° C. using 25 mm parallel plate geometry under N₂ atmosphere. In this experiment, a compression molded circular plaque with a thickness of 1.8 mm was placed between the pre-heated upper and lower measurement fixtures and allowed to come to thermal equilibrium. The upper plate was then lowered to 50 μm above the testing gap size of 1.5 mm. At this point, the excess material was trimmed off and the upper fixture was lowered to the measurement gap size. A waiting time of 10 min after sample loading and trimming was applied to avoid residual stresses causing the strain to drift. In the creep experiment, the shear stress was increased instantly from 0 to 20 Pa and the strain was recorded versus time. The sample continued to deform under the constant shear stress and eventually reached a steady rate of straining. Creep data was reported in terms of creep compliance (J(t)) which has the units of reciprocal modulus. The inverse of J(t) slope in the steady creeping regime was used to calculate the zero shear rate viscosity based on the linear regression of the data points in the last 10% time window of the creep experiment.

In order to determine if the sample was degraded during the creep test, frequency sweep experiments under small strain amplitude (10%) were performed before and after creep stage over a frequency range of 0.1-100 rad/s. The difference between the magnitude of complex viscosity at 0.1 rad/s before and after the creep stage was used as an indicator of thermal degradation. The difference should be less than 5% to consider the creep determined zero shear rate viscosity acceptable.

Creep experiments confirmed that Reference Line, shown in FIG. 1, for linear ethylene interpolymers was also valid if the creep determined ηo was used rather than the DMA determined η₀. In this disclosure, the LCBF (Long Chain Branching Factor) was determined using the DMA determined η₀. To be absolutely clear, the zero shear viscosity (ZSV [poise]) data reported in Tables 1A, 2 and 3 were measured using DMA.

¹³C Nuclear Magnetic Resonance (NMR)

Between 0.21 and 0.30 g of polymer sample was weighed into 10 mm NMR tubes. The sample was then dissolved with deuterated ortho-dichlorobenzene (ODCB-d4) and heated to 125° C.; a heat gun was used to assist the mixing process. ¹³C NMR spectra (24000 scans per spectra) were collected on a Bruker AVANCE III HD 400 MHz NMR spectrometer fitted with a 10 mm PABBO probehead maintained at 125° C. Chemical shifts were referenced to the polymer backbone resonance, which was assigned a value of 30.0 ppm. ¹³C spectra were processed using exponential multiplication with a line broadening (LB) factor of 1.0 Hz. They were also processed using Gaussian multiplication with LB=−0.5 Hz and GB=0.2 to enhance resolution.

Short chain branching was calculated using the isolated method, where the integral area of peaks unique to that branch length are compared to the total integral (standard practice for branches up to and including C5). Quantitative data for the C1, C2, C3, C4, (C6+LCB) and the Saturated Termini (Sat. Term.) carbons was presented in Table 14, all values reported per 1000 total carbon atoms, data accuracy was ±0.03 branches/1000C. Any values of 0.03 branches/1000C or less were assumed beyond the ability to quantify and were marked with a ‘D’ to indicate that a peak was detected but not quantifiable in Table 14.

FIG. 3 diagrams a long chain branched macromolecule on the left and a C6 branched macromolecule on the right and the nomenclature, or code, used to identify each carbon atom that appears in the ¹³C-NMR spectrum of these macromolecules. Branchpoint carbons peaks (CH_((L)) and CH₍₆₎, 38.2 ppm), as well as the 1B_(L)/1B₆, 2B_(L)/2B₆ and 3B_(L)/3B₆ carbon peaks (at 14.1, 22.9, and 32.2 ppm, respectively) are close together in the spectrum. Additionally, the ends of a LCB are functionally equivalent to the ends of macromolecular chains. In ethylene-octene copolymers there was separation between the 2B₆ and 3B₆ peaks and the 2s & 3s peaks in the chain termini. With the goal of deconvoluting the C6 and LCB contributions to the branchpoint peak (38.2 ppm), the spectra were reprocessed using a Gaussian function (as opposed to an exponential function), specifically LB=−0.5 and GB=0.2. The net effect of this reprocessing was to ‘trade off’ some signal/noise (S/N) for additional resolution without negatively impacting peak integration, i.e. quantification of the respective carbons. Using this technique, the values for C6, LCB and saturated termini were obtained using the following method: 1) the values for (C6+LCB) peak at 38.2 ppm and the two (LCB+sat. term.) peaks at 32.2 and 22.9 ppm were calculated from the ‘standard’ spectrum; 2) these three peak regions in the Gaussian reprocessed spectra (i.e. 38.2, 32.2 and 22.9 ppm) were integrated to obtain a ratio for each carbon within the respective peak; 3) these ratios were converted to a value per 1000 carbons by normalizing by the respective integrated area measured in step 1); 4) the saturated termini was the average of that from 2s & 3s peaks; 5) the C6 value was estimated from the integrals of the small peaks on the far left of these three regions, and; 6) the LCB value was estimated from the peak at 38.2 ppm.

Film Dart Impact

Film dart impact strength was determined using ASTM D1709-09 Method A (May 1, 2009). In this disclosure the dart impact test employed a 1.5 inch (38 mm) diameter hemispherical headed dart.

Film Puncture

Film “puncture”, the energy (J/mm) required to break the film was determined using ASTM D5748-95 (originally adopted in 1995, reapproved in 2012).

Film Lubricated Puncture

The “lubricated puncture” test was performed as follows: the energy (J/mm) to puncture a film sample was determined using a 0.75-inch (1.9-cm) diameter pear-shaped fluorocarbon coated probe travelling at 10-inch per minute (25.4-cm/minute). ASTM conditions were employed. Prior to testing the specimens, the probe head was manually lubricated with Muko Lubricating Jelly to reduce friction. Muko Lubricating Jelly is a water-soluble personal lubricant available from Cardinal Health Inc., 1000 Tesma Way, Vaughan, ON L4K 5R8 Canada. The probe was mounted in an Instron Model 5 SL Universal Testing Machine and a 1000-N load cell as used. Film samples (1.0 mil (25 μm) thick, 5.5 inch (14 cm) wide and 6 inch (15 cm) long) were mounted in the Instron and punctured.

Film Tensile

The following film tensile properties were determined using ASTM D882-12 (Aug. 1, 2012): tensile break strength (MPa), elongation at break (%), tensile yield strength (MPa), tensile elongation at yield (%) and film toughness or total energy to break (ft·lb/in³). Tensile properties were measured in the both the machine direction (MD) and the transverse direction (TD) of the blown films.

Film Secant Modulus

The secant modulus is a measure of film stiffness. Secant moduli were determined according to ASTM D882. The secant modulus is the slope of a line drawn between two points on the stress-strain curve, i.e. the secant line. The first point on the stress-strain curve is the origin, i.e. the point that corresponds to the origin (the point of zero percent strain and zero stress), and; the second point on the stress-strain curve is the point that corresponds to a strain of 1%; given these two points the 1% secant modulus is calculated and is expressed in terms of force per unit area (MPa). The 2% secant modulus is calculated similarly. This method is used to calculated film modulus because the stress-strain relationship of polyethylene does not follow Hook's law; i.e. the stress-strain behavior of polyethylene is non-linear due to its viscoelastic nature. Secant moduli were measured using a conventional Instron tensile tester equipped with a 200 lbf load cell. Strips of monolayer film samples were cut for testing with following dimensions: 14 inch long, 1 inch wide and 1 mil thick; ensuring that there were no nicks or cuts on the edges of the samples. Film samples were cut in both the machine direction (MD) and the transverse direction (TD) and tested. ASTM conditions were used to condition the samples. The thickness of each film was accurately measured with a hand-held micrometer and entered along with the sample name into the Instron software. Samples were loaded in the Instron with a grip separation of 10 inch and pulled at a rate of 1 inch/min generating the strain-strain curve. The 1% and 2% secant modulus were calculated using the Instron software.

Film Puncture-Propagation Tear

Puncture-propagation tear resistance of blown film was determined using ASTM D2582-09 (May 1, 2009). This test measures the resistance of a blown film to snagging, or more precisely, to dynamic puncture and propagation of that puncture resulting in a tear. Puncture-propagation tear resistance was measured in the machine direction (MD) and the transverse direction (TD) of the blown films.

Film Elmendorf Tear

Film tear performance was determined by ASTM D1922-09 (May 1, 2009); an equivalent term for tear is “Elmendorf tear”. Film tear was measured in both the machine direction (MD) and the transverse direction (TD) of the blown films.

Film Opticals

Film optical properties were measured as follows: Haze, ASTM D1003-13 (Nov. 15, 2013), and; Gloss ASTM D2457-13 (Apr. 1, 2013).

Film Dynatup Impact

Instrumented impact testing was carried out on a machine called a Dynatup Impact Tester purchased from Illinois Test Works Inc., Santa Barbara, Calif., USA; those skilled in the art frequently call this test the Dynatup impact test. Testing was completed according to the following procedure. Test samples are prepared by cutting about 5 inch (12.7 cm) wide and about 6 inch (15.2 cm) long strips from a roll of blown film; film was about 1 mil thick. Prior to testing, the thickness of each sample was accurately measured with a handheld micrometer and recorded. ASTM conditions were employed. Test samples were mounted in the 9250 Dynatup Impact drop tower/test machine using the pneumatic clamp. Dynatup tup #1, 0.5 inch (1.3 cm) diameter, was attached to the crosshead using the Allen bolt supplied. Prior to testing, the crosshead is raised to a height such that the film impact velocity is 10.9±0.1 ft/s. A weight was added to the crosshead such that: 1) the crosshead slowdown, or tup slowdown, was no more than 20% from the beginning of the test to the point of peak load and 2) the tup must penetrate through the specimen. If the tup does not penetrate through the film, additional weight is added to the crosshead to increase the striking velocity. During each test the Dynatup Impulse Data Acquisition System Software collected the experimental data (load (lb) versus time). At least 5 film samples are tested and the software reports the following average values: “Dynatup Maximum (Max) Load (lb)”, the highest load measured during the impact test; “Dynatup Total Energy (ft·lb)”, the area under the load curve from the start of the test to the end of the test (puncture of the sample), and; “Dynatup Total Energy at Max Load (ft·lb)”, the area under the load curve from the start of the test to the maximum load point.

Film Hot Tack

In this disclosure, the “Hot Tack Test” was performed as follows, using ASTM conditions. Hot tack data was generated using a J&B Hot Tack Tester which is commercially available from Jbi Hot Tack, Geloeslaan 30, B-3630 Maamechelen, Belgium. In the hot tack test, the strength of a polyolefin to polyolefin seal is measured immediately after heat sealing two film samples together (the two film samples were cut from the same roll of 2.0 mil (51-μm) thick film), i.e. when the polyolefin macromolecules that comprise the film are in a semi-molten state. This test simulates the heat sealing of polyethylene films on high speed automatic packaging machines, e.g., vertical or horizontal form, fill and seal equipment. The following parameters were used in the J&B Hot Tack Test: film specimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; film sealing pressure, 0.27 N/mm²; delay time, 0.5 second; film peel speed, 7.9 in/second (200 mm/second); testing temperature range, 203° F. to 293° F. (95° C. to 145° C.); temperature increments, 9° F. (5° C.); and five film samples were tested at each temperature increment to calculate average values at each temperature. The following data was recorded for the disclosed Example films and Comparative Example films: the “Tack Onset@1.0 N (° C.)”, the temperature at which a hot tack force of 1N was observed (average of 5-film samples); “Max Hot tack Strength (N)”, the maximum hot tack force observed (average of 5-film samples) over, the testing temperature range, and; “Temperature−Max. Hot tack (° C.)”, the temperature at which the maximum hot tack force was observed.

Film Heat Seal Strength

In this disclosure, the “Heat Seal Strength Test” was performed as follows. ASTM conditions were employed. Heat seal data was generated using a conventional Instron Tensile Tester. In this test, two film samples are sealed over a range of temperatures (the two film samples were cut from the same roll of 2.0 mil (51-μm) thick film). The following parameters were used in the Heat Seal Strength Test: film specimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; film sealing pressure, 40 psi (0.28 N/mm²); temperature range, 212° F. to 302° F. (100° C. to 150° C.) and temperature increment, 9° F. (5° C.). After aging for at least 24 hours at ASTM conditions, seal strength was determined using the following tensile parameters: pull (crosshead) speed, 12 inch/min (2.54 cm/min); direction of pull, 90° to seal, and; 5 samples of film were tested at each temperature increment. The Seal Initiation Temperature, hereinafter S.I.T., is defined as the temperature required to form a commercially viable seal; a commercially viable seal has a seal strength of 2.0 lb per inch of seal (8.8 N per 25.4 mm of seal).

Film Hexane Extractables

Hexane extractables was determined according to the Code of Federal Registration 21 CFR § 177.1520 Para (c) 3.1 and 3.2; wherein the quantity of hexane extractable material in a film is determined gravimetrically. Elaborating, 2.5 grams of 3.5 mil (89 vim) monolayer film was placed in a stainless steel basket, the film and basket were weighed (w^(i)). While in the basket the film was: extracted with n-hexane at 49.5° C. for two hours; dried at 80° C. in a vacuum oven for 2 hours; cooled in a desiccator for 30 minutes, and; weighed (w^(f)). The percent loss in weight is the percent hexane extractables (w^(C6)): w^(C6)=100×(w^(i)−w^(f))/w^(i).

EXAMPLES

Pilot Plant Polymerizations

The following examples are presented for the purpose of illustrating selected embodiments of this disclosure, it being understood that, the examples presented hereinafter do not limit the claims presented.

Disclosed embodiments of the ethylene interpolymer products were prepared in a continuous solution pilot plant operated in both series mode and parallel mode as fully described below. Comparative ethylene interpolymer products were also prepared in the same pilot plant.

Series Polymerization

Series mode Example 50 and Example 51 of ethylene interpolymer products and series mode Comparative 60, shown in Tables 4A through 4C, were produced using an R1 pressure from about 14 MPa to about 18 MPa; R2 was operated at a lower pressure to facilitate continuous flow from R1 to R2. In series mode the first exit stream from R1 flows directly into R2. Both CSTR's were agitated to give conditions in which the reactor contents were well mixed. The process was operated continuously by feeding fresh process solvent, ethylene, 1-octene and hydrogen to the reactors. Methylpentane was used as the process solvent (a commercial blend of methylpentane isomers). The volume of the first CSTR reactor (R1) was 3.2 gallons (12 L), the volume of the second CSTR reactor (R2) was 5.8 gallons (22 L) and the volume of the tubular reactor (R3) was 0.58 gallons (2.2 L).

The following components were used to prepare the first homogeneous catalyst formulation that was injected into R1, i.e. the bridged metallocene catalyst formulation comprising: a component A, either diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafnium dichloride [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂] (abbreviated CpF-1) or diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafnium dimethyl, [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂] (abbreviated CpF-2); component M, methylaluminoxane (MMAO-07); component B, trityl tetrakis(pentafluoro-phenyl)borate, and; component P, 2,6-di-tert-butyl-4-ethylphenol. As shown in Table 4A, CpF-1 was used to produce Example 50 and CpF-2 was used to produce Examples 51 and 52. To prepare the bridged metallocene catalyst formulation the following catalyst component solvents were used: methylpentane for components M and P, and; xylene for component A and B.

Comparative ethylene interpolymer products were prepare by injecting the third homogeneous catalyst formulation into R1. In Comparative ethylene interpolymer products the third homogeneous catalyst formulation replaces the first homogeneous catalyst formulation. One embodiment of the third homogeneous catalyst formulation was an unbridged single site catalyst formulation comprising: component C, either cyclopentadienyl tri(tertiary butyl)phosphinimine titanium dichloride [Cp[(t-Bu)₃PN]TiCl₂] (abbreviated PIC-1) or cyclopentadienyl tri(isopropyl)phosphinimine titanium dichloride [Cp[(isopropyl)₃PNITiCl₂] (abbreviated PIC-2); component M, methylaluminoxane (MMAO-07); component B, trityl tetrakis(pentafluoro-phenyl)borate, and; component P, 2,6-di-tert-butyl-4-ethylphenol. As shown in Table 4A, PIC-2 was used to produce Comparative 60 and PIC-1 was used to produce Comparative 61. To prepare the unbridged single site catalyst formulation the following catalyst component solvents were used: methylpentane for components M and P, and; xylene for component A and B.

The quantity of CpF-1 or CpF-2 added to reactor 1 (R1) is shown in Table 4A, e.g. “R1 catalyst (ppm)” was 0.72 ppm of CpF-1 in the case of Example 50. The efficiency of the first homogeneous catalyst formulation was optimized by adjusting the mole ratios of the catalyst components and the R1 catalyst inlet temperature. As shown in Table 4A, the mole ratios optimized were: ([M]/[A]), i.e. [(MMAO-07)/(CpF-1)]; ([P]/[M]), i.e. [(2,6-di-tert-butyl-4-ethylphenol)/(MMAO-07)], and; ([B]/[A]), i.e. [(trityl tetrakis(pentafluoro-phenyl)borate)/(CpF-1)]. To be more clear, in Example 50 (Table 4A), the mole ratios in R1 were: ([M]/[A])=122; ([P]/[M])=0.40, and; ([B]/[A])=1.47. As shown in Table 4C, the catalyst inlet temperature of the bridged metallocene catalyst formulation was: about 145° C. in the case of CpF-1, and; about 21 to about 25° C. in the case of CpF-2.

In the Comparatives the quantity of PIC-1 or PIC-2 added to reactor 1 (R1) is shown in Table 4A, e.g. “R1 catalyst (ppm)” was 0.14 ppm of PIC-2 in the case of Comparative 60. The efficiency of the third homogeneous catalyst formulation was optimized by adjusting the mole ratios of the catalyst components and the R1 catalyst inlet temperature. As shown in Table 4A, the mole ratios optimized were: ([M]/[C]), i.e. (MMAO-07)/(PIC-2); ([P]/[M]), i.e. (2,6-di-tert-butyl-4-ethylphenol)/(MMAO-07), and; ([B]/[C]), i.e. (trityl tetrakis(pentafluoro-phenyl)borate)/(PIC-2). To be more clear, as shown in Table 4A, in Comparative 60 the mole ratios in R1 were: ([M]/[C])=65; ([P]/[M])=0.30, and; ([B]/[C])=1.20. As shown in Table 4C, the R1 catalyst inlet temperature of the unbridged single site catalyst formulation was about 30 to about 32° C.

In both Examples and Comparatives a second homogeneous catalyst formulation was injected into the second reactor (R2), e.g. an unbridged single site catalyst formulation, PIC-1 or PIC-2 as specified in Table 4A.

Average residence time of the solvent in a reactor is primarily influenced by the amount of solvent flowing through each reactor and the total amount of solvent flowing through the solution process, the following are representative or typical values for the Examples and Comparatives shown in Tables 4A-4C, as well as Examples shown in Tables 6A-6C: average reactor residence times were: about 61 seconds in R1, about 73 seconds in R2, about 7.3 seconds for an R3 volume of 0.58 gallons (2.2 L).

Polymerization in the continuous solution polymerization process was terminated by adding a catalyst deactivator to the third exit stream exiting the tubular reactor (R3). The catalyst deactivator used was octanoic acid (caprylic acid), commercially available from P&G Chemicals, Cincinnati, Ohio, U.S.A. The catalyst deactivator was added such that the moles of fatty acid added were 50% of the total molar amount of hafnium, titanium and aluminum added to the polymerization process; to be clear, the moles of octanoic acid added=0.5×(moles hafnium+moles titanium+moles aluminum); this mole ratio was consistently used in both Examples and Comparatives.

A two-stage devolitizing process was employed to recover the ethylene interpolymer product from the process solvent, i.e. two vapor/liquid separators were used and the second bottom stream (from the second V/L separator) was passed through a gear pump/pelletizer combination.

Prior to pelletization the ethylene interpolymer product was stabilized by adding 500 ppm of Irganox 1076 (a primary antioxidant) and 500 ppm of Irgafos 168 (a secondary antioxidant), based on weight of the ethylene interpolymer product. Antioxidants were dissolved in process solvent and added between the first and second V/L separators.

Tables 4A-4C disclose additional process parameters, e.g. ethylene and 1-octene splits between the reactors, and reactor temperatures and ethylene conversions, etc. In Tables 4A-4C the targeted ethylene interpolymer product was about 1.0 dg/min (melt index (I₂), as measured according to ASTM D1239, 2.16 kg load,190° C.) and about 0.917 g/cm³ (as measured according to ASTM D792).

Tables 6A-6C disclose continuous solution process parameters for Example 58 (about 4 dg/min (I₂) and about 0.928 g/cc) and Example 59 (about 0.24 dg/min (I₂) and about 0.944 g/cc).

Parallel Polymerization

The pilot plant described above was reconfigured to operate in parallel mode. In parallel mode the first exit stream (exiting the first reactor) by-passes the second reactor and the first exit stream is combined with the second exit stream (exiting the second reactor) downstream of the second reactor. To be more clear, FIG. 2 illustrates parallel mode operation where: the first exit stream 11 g (dotted line) by-passes the second reactor 12 a, streams 11 g and stream 12 c (second exit stream from reactor 12 a) are combined to form a third exit stream 12 d, and; the third exit stream flows into the tubular reactor 17. As shown in Tables 4A through 4C, Example 52 is one embodiment of an ethylene interpolymer product synthesized using parallel mode operation. Catalyst optimization and additional process parameters for Example 52, e.g. ethylene and 1-octene splits between the reactors, and reactor temperatures and ethylene conversions, etc., are summarized in Tables 4A-4C.

Given the continuous solution polymerization conditions shown in Table 4A through Table 4C, the physical properties of the resulting ethylene interpolymer products are summarized in Table 5, i.e. Examples 50-52. Table 5 also discloses the physical properties of Comparatives 60, 61 and 67. Comparative 67 was a commercially available solution process ethylene/1-octene polymers produced by NOVA Chemicals Company (Calgary, Alberta, Canada) SURPASS° FPs117-C, produced using the unbridged single site catalyst formulation in rectors 1 and 2. As shown in Table 5, Neutron Activation Analysis results disclose catalyst residues in Examples 51 and 52 and Comparatives 60, 61 and 67. Given the continuous solution polymerization conditions shown in Tables 6A through 6C, the resulting ethylene interpolymer products produced are summarized in Table 7, i.e. Examples 58 and 59.

Table 8 compares physical attributes of Example 51 with Comparative 67, i.e. the weight fractions, molecular weights (M_(n), M_(w) and M_(w)/M_(n)), branching (#C6/1000C), CDBI₅₀, density, melt index and long chain branching factor (LDBF) of the first ethylene interpolymer, second ethylene interpolymer, third ethylene interpolymer and the ethylene interpolymer product are disclosed. Results in Table 8 were generated by deconvoluting the SEC and CTREF curves of Example 51 and Comparative 67 into their respective components. Graphically, FIG. 4 illustrates the deconvolution of the experimentally measured SEC of Example 51 into three components, i.e. the first, second and third ethylene interpolymer. In Example 51 the first ethylene interpolymer having a density of 0.8940 g/cm³ was produced using an ((1-octene)/(ethylene))^(R1) weight ratio of 0.41. In contrast, in Comparative 67 the first ethylene interpolymer density having a density of 0.9141 g/cm³ was produced using an ((1-octene)/(ethylene))^(R1) weight ratio of 1.43. Even though Example 51 was produced with a 71% lower octene/ethylene ratio, relative to Comparative 67, the first ethylene interpolymer in Example 51 was of lower density. Both of these trends shown by Example 51 employing the bridged metallocene catalyst formulation, i.e. a lower (octene/ethylene) ratio and a lower density are advantageous, relative to Comparative 67 employing the unbridged single site catalyst formulation. Table 8 also discloses a Δρ, (ρ²−ρ¹) or [(the density of the second ethylene interpolymer)−(the density of the first ethylene interpolymer)], was higher in Example 51 relative to Comparative 67. Specifically, Δρ was 0.0473 and 0.0040 g/cm³ for Example 51 and Comparative 67, respectively. Higher Δρ's are advantageous in several end-use applications. In FIG. 4: the molecular weight distribution of the first, second and third ethylene interpolymers were assumed similar to Flory distributions. The weight percent of the third ethylene interpolymer was assumed to be 5%.

As shown in Table 8, the weight average molecular weights (M_(w)) of the first ethylene interpolymers in Example 51 and Comparative 67 were 141,247 and 165,552, respectively. The lower M_(w) of the first ethylene interpolymer in Example 51 reflects the fact that reactor 1 contained 5.35 ppm of hydrogen; in contrast, in Comparative 67 the first ethylene interpolymer was synthesized using 0.60 ppm of hydrogen in reactor 1. Those of ordinary experience are cognizant of the fact that hydrogen is used to control M_(w) (or melt index) in olefin polymerization, i.e. hydrogen is very effective in terminating propagating macromolecules. Further, given Table 8, those of ordinary experience would have recognized the higher molecular weight capability of the bridged metallocene catalyst relative to the unbridged single site catalyst. Elaborating, relative to Comparative 67, the amount of hydrogen used to synthesize the first ethylene interpolymer in Example 51 was about an order of magnitude higher, and yet the M_(w)'s differed by only 15%. This trend of higher hydrogen concentration for the bridged metallocene catalyst formulation, relative to the unbridged single site catalyst formulation, demonstrated the higher molecular weight capability of the former. Example 51 and Comparative 67 were produced at similar reactor temperatures, i.e. 139.5° C. and 140.0° C., respectively.

Blown Films: Ethylene Interpolymer Products

Monolayer blown films were produced on a Gloucester extruder, 2.5 inch (6.45 cm) barrel diameter, 24/1 L/D (barrel Length/barrel Diameter) equipped with: a barrier screw; a low pressure 4 inch (10.16 cm) diameter die with a 35 mil (0.089 cm) die gap, and; a Western Polymer Air ring. Blown films, 1.0 mil (25 μm) thick, were produced at a constant output rate of 100 lb/hr (45.4 kg/hr) by adjusting extruder screw speed, and; the frost line height was maintained at about 16 inch (40.64 cm) by adjusting the cooling air. Blown film processing conditions for Examples 51 and 52 and Comparative 67 are disclosed in Table 9. Monolayer blown film was also produced at 2.0 mil (51 μm) and 3.5 mil (89 μm) to determine the seal initiation temperature (SIT) and hexane extractables, respectively. Processing aid, encapsulated in a polyethylene masterbatch, was added to all resins prior to film extrusion; the processing aid added was Dynamar FX 5920A (commercially available from The 3M Company, St. Paul, Minn., USA).

As shown in Table 9, in blown film processes, Examples 51 and 52 have improved processability relative to Comparative 67, i.e. lower extrusion pressures and lower extruder current draw. Improved processability is desirable to the film converter because improved processability means higher production rates, e.g. an increase in the pounds of film produced per hour, or feet (meters) of film produced per hour.

As shown in Table 10A, relative to Comparative 67, blown films produced from Examples 51 and 52 can be advantageously used in any film application where improved film hexane extractables are desired, e.g. in food packaging applications. The hexane extractables of a blown film, Example 51F, prepared from Example 51 were: 65% lower relative to Comparative 67. The hexane extractables of a blown film, Example 52F, prepared from Example 52 were: 54% lower relative to Comparative 67.

As shown in Table 10A, the seal initiation temperature (SIT) of Example 51F film (produced in a series solution process) was 93.6° C.; which was improved (i.e. lower by 6%) relative to Comparative 67's SIT of 99.1° C. The seal initiation temperature (SIT) of Example 52F film (produced in a parallel solution process) was 89.1° C.; which was improved (i.e. lower by 10%) relative to Comparative 67's SIT of 99.1° C. As shown in Table 10A, the Tack Onset (at 1.0N) of film Examples 51F and 52F were 90 and 86° C., respectively; which were improved (i.e. lower by 11% and 15%, respectively) relative to film Comparative 67F's SIT of 101° C. As shown in Table 10A, the temperature at which the maximum Hot Tack was observed was 105 and 100° C. for film Examples 51F and 52F, respectively, which can be compared to Comparative 67F's 115° C. value. To be clear, the temperature at maximum Hot Tack of film 51F was improved (lower) by 9%, relative to Comparative 67F; similarly the temperature at maximum Hot Tack of film 52F was improved by 13%, relative to Comparative 67F. Lower SIT's, lower Tack onset and a lower temperature at maximum Hot Tack are desirable in food packaging applications, e.g. high speed vertical form-fill-seal food packaging lines.

As shown in Table 10A, the machine direction Elmendorf tear strength of film Example 52F was 288 g was similar to film Comparative 67F machine direction Elmendorf tear strength of 282 g. The transverse direction Elmendorf tear strength of film Example 52F was 568 g; i.e. improved (higher by 12%) relative to film Comparative 67F transverse direction Elmendorf film tear strengths of 507 g. The dart impact of Example 51F (series configuration) was 800 g, i.e. improved by 100% relative to Comparative 67F dart impact of 400 g.

As shown in Table 10B, relative to Comparative 67F, blown films produced from Examples 51F and 52F can be advantageously used in film application where higher film moduli are desired. One of the desirable features of higher film moduli is the ability to reduce film thickness, reducing film thickness contributes to source reduction, sustainability and reduces overall costs. The machine direction 1% secant modulus of Example 51F (212 MPa) was 29% improved (higher) relative to Comparative 67F (164 MPa), and; the transverse direction 1% secant modulus of Example 51F (255 MPa) was 58% improved relative to Comparative 67F (161 MPa). The machine direction 1% secant modulus of Example 52F (228 MPa) was 39% improved (higher) relative to Comparative 67F, and; the transverse direction 1% secant modulus of Example 52F (258 MPa) was 60% improved relative to Comparative 67F. This same trend was also evident in the 2% secant modulus. Specifically, the machine direction 2% secant modulus of Example 51F (178 MPa) was 25% improved (higher) relative to Comparative 67F (142 MPa), and; the transverse direction 2% secant modulus of Example 51F (211 MPa) was 54% improved relative to Comparative 67F (137 MPa). Similarly, the machine direction 2% secant modulus of Example 52F (190 MPa) as 33% improved (higher) relative to Comparative 67F, and; the transverse direction 2% secant modulus of Example 52F (215 MPa) was 57% improved relative to Comparative 67F. Table 10B also shows improved (higher) tensile yield strength for Examples 51F and 52F, relative to Comparative 67F. Higher yield strengths reduce the tendency of a loaded package to yielding, deform or distort under its own weight. The machine direction tensile yield strength of Example 51F was 10.2 MPa, which was 12% improved (higher) relative to Comparative 67F (9.1 MPa), and; the transverse direction tensile yield strength of Example 51F (11.4 MPa) was 31% improved relative to Comparative 67F (8.7 MPa). The machine direction tensile yield strength of Example 52F was 10.5 MPa, which was 15% improved (higher) relative to Comparative 67F, and; the transverse direction tensile yield strength of Example 52F (11.5 MPa) was 32% improved relative to Comparative 67F.

As shown in Table 10B, the blown film produced from Example 52 (parallel mode) had a higher (21% improved) film toughness (Total Energy to Break TD) of 1605 ft·lb/in³, relative to the blown film produced from Comparative 67 (series mode) having a film toughness of 1327 ft·lb/in³.

Continuous Polymerization Unit (CPU)

Comparison of Catalyst Formulations in One Reactor

Small scale continuous solution polymerizations were conducted on a Continuous Polymerization Unit, hereinafter CPU. The purpose of these experiments were to directly compare the performance of the bridged metallocene catalyst formulation (containing component A, CpF-1) with the unbridged single site catalyst formulation (containing component C, PIC-1) in one reactor.

The single reactor of the CPU was a 71.5 mL continuously stirred CSTR, polymerizations were conducted at 130° C., 160° C. or 190° C. and the reactor pressure was about 10.5 MPa. The CPU included a 20 mL upstream mixing chamber that was operated at a temperature that was 5° C. lower than the downstream polymerization reactor. The upstream mixing chamber was used to pre-heat the ethylene, optional α-olefin and a portion of the process solvent. Catalyst feeds and the remaining solvent were added directly to the polymerization reactor as a continuous process. The total flow rate to the polymerization reactor was held constant at 27 mL/minute. The components of the bridged metallocene catalyst formulation (component A, component M, component B and component P) were added directly to the polymerization reactor to maintain the continuous polymerization process. More specifically: component A and component B were premixed in xylene and injected directly into the reactor, and; component M and optionally component P were premixed in process solvent and injected directly into the reactor. In the comparative experiments, the components of the unbridged single site catalyst formulation (component C, component M, component B and component P) were added directly to the polymerization reactor to maintain the continuous polymerization process. More specifically: component C and component B were premixed in xylene and injected directly into the reactor, and; component M and optionally component P were premixed in process solvent and injected directly into the reactor. In the examples, the component A employed was CpF-1 [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂]. In the comparatives, the component C employed was PIC-1 ([Cp[(t-Bu)₃PN]TiCl₂]). Components M, B and P were methylaluminoxane (MMAO-07), trityl tetrakis(pentafluoro-phenyl)borate, and 2,6-di-tert-butyl-4-ethylphenol, respectively. Upon injection, the catalyst was activated in situ (in the polymerization reactor) in the presence of ethylene and optional α-olefin comonomer. Component M was added such that the mole ratio of ([M]/[A]) or ([M]/[C]) was about 80; component B was added such that the mole ratio of ([M]/[A]) or ([M]/[C]) was about 1.0, and; component P was added such that the mole ratio of ([P]/[M]) was about 0.4.

Ethylene was supplied to the reactor by a calibrated thermal mass flow meter and was dissolved in the reaction solvent prior to the polymerization reactor. Optional comonomer (1-octene) was premixed with ethylene before entering the polymerization reactor, the (1-octene)/(ethylene) weight ratio varied from 0 to about 6.0. Ethylene was fed to the reactor such that the ethylene concentration in the reactor varied from about 7 to about 15 weight %; where weight % is the weight of ethylene divided by the total weight of the reactor contents. The internal reaction temperature was monitored by a thermocouple in the polymerization medium and was controlled at the target set point to ±0.5° C. Solvent, monomer, and comonomer streams were all purified by the CPU systems prior to entering the reactor.

The ethylene conversion, Q^(CPU), i.e. the fraction of ethylene converted was determined by an online gas chromatograph (GC) and polymerization activity, K_(p) ^(CPU), having dimensions of [L/(mmol·min)] was defined as:

$K_{p}^{CPU} = {Q^{CPU}\left( \frac{1 - Q^{CPU}}{\lbrack{catalyst}\rbrack \times {HUT}^{CPU}} \right)}$ where HUT^(CPU) was a reciprocal space velocity (Hold Up Time) in the polymerization reactor having dimensions of minutes (min), and; [catalyst] was the concentration of catalyst in the polymerization reactor expressed in mmol/L of titanium or hafnium. In some CPU experiments, Q^(CPU) was held constant at about 90% and the HUT^(CPU) was held constant at about 2.5 minutes. In other CPU experiments, Q^(CPU) was varied from about 75 to about 95%. Downstream of the reactor the pressure was reduced to atmospheric pressure. The polymer product was recovered as a slurry in the process solvent and subsequently dried by evaporation in a vacuum oven prior to characterization.

At a polymerization temperature of 130° C., the CPU conditions were adjusted to synthesize ethylene interpolymers at approximately constant melt index and density; specifically, a first ethylene interpolymer synthesized with the bridged metallocene catalyst formulation and a comparative ethylene interpolymer produced with the unbridged single site catalyst formulation. As shown by each row in Table 11A, at a reactor temperature of 130° C., the bridged metallocene catalyst formulation produced an improved (higher) SEC weight average molecular weight (M_(w) ^(A)), relative to the comparative unbridged single site catalyst formulation (M_(w) ^(C)). The percent improvement in M_(w) was at least 5% as calculated using the following formula: % Improved M _(w)=100%×(M _(w) ^(A) −M _(w) ^(C))/M _(w) ^(C)

Similarly, at a polymerization temperature of 160° C., each row of Table 11B shows that the bridged metallocene catalyst formulation produced an improved (higher) SEC weight average molecular weight (M_(w) ^(A)), relative to the comparative unbridged single site catalyst formulation (M_(w) ^(C)). The percent improvement in M_(w) was at least 10%.

As shown in Table 12A, at a polymerization temperature of 130° C., the (α-olefin/ethylene) weight ratio in the reactor had to be adjusted such that ethylene interpolymers were produced having a target density. More specifically, (α-olefinIethylene)^(A) was required to synthesize a first ethylene interpolymer, having a target density, using the bridged metallocene catalyst formulation. In contrast, (α-olefinlethylene)^(C) was required to synthesize a control ethylene interpolymer, having the target density, using the unbridged single site catalyst formulation. As shown by each row in Table 12A, at 130° C., the bridged metallocene catalyst formulation allows the operation of the continuous solution polymerization process at an improved (reduced) (α-olefin/ethylene) weight ratio, relative to the control unbridged single site catalyst formulation. The percent reduction in (α-olefin/ethylene) weight ratio was at least −70% as calculated using the following formula:

${\%\mspace{14mu}{{Reduced}\mspace{14mu}\left\lbrack \frac{\alpha - {olefin}}{ethylene} \right\rbrack}} = {{100 \times \left\{ \frac{\left( \frac{\alpha - {olefin}}{ethylene} \right)^{A} - \left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}}{\left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}} \right\}} \leq {{- 70}\%}}$

Similarly, at a polymerization temperature of 160° C., each row of Table 12B shows that the bridged metallocene catalyst formulation allows the operation of the continuous solution polymerization process at an improved (reduced) (α-olefin/ethylene) weight ratio, relative to the control unbridged single site catalyst formulation. In Table 12B, the percent reduction in (α-olefin/ethylene) weight ratio was at least −70%.

CPU experiments were also conducted to collect samples of the first ethylene interpolymer produced with the bridged metallocene catalyst formulation for ¹³C NMR characterization to quantify the amount of long chain branching (LCB). Table 13 summarizes typical CPU process conditions at three reactor temperatures (130, 160 and 190° C.) and two levels of ethylene conversion (about 75 wt % and about 95 wt %). Polymer characterization data (of the first ethylene interpolymer produced with the bridged metallocene catalyst formulation) is summarized in Table 14, the level of long chain branching in the ethylene interpolymers produced with the bridged metallocene catalyst formulation varied from 0.03 to 0.23 long chain branches (LCB) per 1000 carbon atoms.

TABLE 1A Reference resins (linear ethylene polymers) containing undetectable levels of Long Chain Branching (LCB). Reference Mv [η] SCBD Resins (g/mole) (dL/g) M_(w)/M_(n) A CH₃#/1000C ZSV (poise) Resin 1 1.06E+05 1.672 2.14 1.9772 10.5 7.81E+04 Resin 2 1.11E+05 1.687 2.00 1.9772 11.2 7.94E+04 Resin 3 1.06E+05 1.603 1.94 1.9772 15.9 7.28E+04 Resin 4 1.07E+05 1.681 1.91 1.9772 11.0 8.23E+04 Resin 5 7.00E+04 1.192 2.11 1.9772 13.7 1.66E+04 Resin 6 9.59E+04 1.497 1.88 1.9772 12.6 5.73E+04 Resin 7 1.04E+05 1.592 1.85 1.9772 12.8 6.60E+04 Resin 8 5.09E+04 0.981 2.72 2.1626 0.0 6.42E+03 Resin 9 5.27E+04 0.964 2.81 2.1626 0.0 6.42E+03 Resin 10 1.06E+05 1.663 1.89 1.1398 13.3 7.69E+04 Resin 11 1.10E+05 1.669 1.81 1.1398 19.3 7.31E+04 Resin 12 1.07E+05 1.606 1.80 1.1398 27.8 6.99E+04 Resin 13 6.66E+04 1.113 1.68 2.1626 17.8 1.39E+04 Resin 14 6.62E+04 1.092 1.76 2.1626 21.4 1.45E+04 Resin 15 6.83E+04 1.085 1.70 2.1626 25.3 1.44E+04 Resin 16 7.66E+04 1.362 2.51 2.1626 4.0 3.24E+04 Resin 17 6.96E+04 1.166 2.53 2.1626 13.9 2.09E+04 Resin 18 6.66E+04 1.134 2.54 2.1626 13.8 1.86E+04 Resin 19 5.81E+04 1.079 2.44 2.1626 5.8 1.10E+04 Resin 20 7.85E+04 1.369 2.32 2.1626 3.7 3.34E+04 Resin 21 6.31E+04 1.181 2.26 2.1626 4.3 1.61E+04 Resin 22 7.08E+04 1.277 2.53 2.1626 3.6 2.58E+04 Resin 23 9.91E+04 1.539 3.09 2.1626 14.0 8.94E+04 Resin 24 1.16E+05 1.668 3.19 2.1626 13.3 1.32E+05 Resin 25 1.12E+05 1.689 2.71 2.1626 12.8 1.38E+05 Resin 26 1.14E+05 1.690 3.37 2.1626 8.0 1.48E+05 Resin 27 9.55E+04 1.495 3.44 2.1626 13.8 8.91E+04 Resin 28 1.00E+05 1.547 3.33 2.1626 14.1 9.61E+04 Resin 29 1.07E+05 1.565 3.52 2.1626 13.0 1.12E+05 Resin 30 1.04E+05 1.525 3.73 2.1626 13.4 1.10E+05 Resin 31 1.10E+05 1.669 3.38 2.1626 8.7 1.26E+05 Resin 32 1.09E+05 1.539 3.42 2.1626 13.4 1.07E+05 Resin 33 8.04E+04 1.474 5.29 2.1626 1.7 7.60E+04 Resin 34 8.12E+04 1.410 7.64 2.1626 0.9 9.11E+04 Resin 35 7.56E+04 1.349 9.23 2.1626 1.0 9.62E+04 Resin 36 7.34E+04 1.339 8.95 2.1626 1.1 1.00E+05 Resin 37 1.01E+05 1.527 3.76 2.1626 13.3 1.11E+05

TABLE 1B Long Chain Branching Factor (LCBF) of reference resins (linear ethylene polymers) containing undetectable levels of Long Chain Branching (LCB). S_(h) S_(v) LCBF (di- (di- (di- Reference Log ZSV_(c) Log IV_(c) mension- mension- mension- Resins (log(poise)) log(dL/g) less) less) less) Resin 1 4.87E+00   2.46E−01 −5.77E−02 −1.21E−02 3.49E−04 Resin 2 4.90E+00   2.52E−01 −5.39E−02 −1.13E−02 3.05E−04 Resin 3 4.87E+00   2.41E−01 −2.46E−02 −5.16E−03 6.33E−05 Resin 4 4.93E+00   2.50E−01 −9.46E−03 −1.99E−03 9.41E−06 Resin 5 4.20E+00   1.07E−01 −6.37E−02 −1.34E−02 4.26E−04 Resin 6 4.78E+00   2.04E−01   5.83E−02   1.22E−02 3.57E−04 Resin 7 4.85E+00   2.31E−01 −1.73E−03 −3.65E−04 3.16E−07 Resin 8 3.69E+00 −8.43E−03 −2.17E−02 −4.55E−03 4.93E−05 Resin 9 3.68E+00 −1.58E−02   1.21E−04   2.44E−05 1.47E−09 Resin 10 4.91E+00   2.38E−01   2.19E−02   4.60E−03 5.04E−05 Resin 11 4.90E+00   2.48E−01 −2.96E−02 −6.21E−03 9.17E−05 Resin 12 4.88E+00   2.42E−01 −1.99E−02 −4.19E−03 4.17E−05 Resin 13 4.21E+00   9.14E−02   2.36E−02   4.96E−03 5.86E−05 Resin 14 4.21E+00   9.22E−02   1.89E−02   3.97E−03 3.75E−05 Resin 15 4.22E+00   1.00E−01 −9.82E−03 −2.06E−03 1.01E−05 Resin 16 4.42E+00   1.44E−01 −1.23E−02 −2.59E−03 1.60E−05 Resin 17 4.23E+00   1.01E−01 −4.64E−03 −9.75E−04 2.26E−06 Resin 18 4.18E+00   8.91E−02   1.66E−03   3.47E−04 2.87E−07 Resin 19 3.97E+00   4.73E−02 −1.09E−02 −2.29E−03 1.25E−05 Resin 20 4.47E+00   1.45E−01   2.28E−02   4.78E−03 5.44E−05 Resin 21 4.16E+00   8.23E−02   1.78E−02   3.73E−03 3.31E−05 Resin 22 4.32E+00   1.15E−01   2.45E−02   5.14E−03 6.30E−05 Resin 23 4.78E+00   2.22E−01 −2.25E−02 −4.73E−03 5.31E−05 Resin 24 4.94E+00   2.56E−01 −3.13E−02 −6.57E−03 1.03E−04 Resin 25 5.02E+00   2.59E−01   3.91E−02   8.21E−03 1.60E−04 Resin 26 4.97E+00   2.48E−01   3.94E−02   8.27E−03 1.63E−04 Resin 27 4.74E+00   2.09E−01 −2.83E−03 −5.95E−04 8.42E−07 Resin 28 4.79E+00   2.24E−01 −3.13E−02 −6.57E−03 1.03E−04 Resin 29 4.83E+00   2.28E−01 −2.96E−03 −6.22E−04 9.20E−07 Resin 30 4.80E+00   2.18E−01   1.47E−02   3.08E−03 2.26E−05 Resin 31 4.90E+00   2.44E−01 −1.40E−02 −2.94E−03 2.06E−05 Resin 32 4.82E+00   2.23E−01   1.27E−02   2.66E−03 1.69E−05 Resin 33 4.51E+00   1.72E−01 −6.37E−02 −1.34E−02 4.26E−04 Resin 34 4.45E+00   1.52E−01 −2.68E−02 −5.62E−03 7.52E−05 Resin 35 4.40E+00   1.33E−01   1.55E−02   3.26E−03 2.53E−05 Resin 36 4.43E+00   1.30E−01   5.82E−02   1.22E−02 3.55E−04 Resin 37 4.80E+00   2.17E−01   1.77E−02   3.71E−03 3.28E−05

TABLE 2 Long Chain Branching Factor (LCBF) of ethylene interpolymer product Examples 50-52 and 58 and Comparatives 60, 61 and 67. Example 50 Example 51 Example 52 Example 58 Comp. 60 Comp. 61 Comp. 67 Mv (g/mole) 1.05E+05 9.09E+04 9.07E+04 5.96E+04 n/a 1.00E+05 9.42E+04 [η] (dL/g) 1.496 1.314 1.340 0.945 n/a 1.538 1.474 Mw/Mn 2.86 2.65 2.04 6.23 2.88 2.37 3.08 A 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 SCB 16.1 15.8 16.2 12.6 13.5 12.1 14.6 (CH₃#/1000C) ZSV (poise) 1.61E+05 1.65E+05 1.77E+05 7.33E+04 1.05E+05 8.06E+04 8.98E+04 Log ZSV_(c) 5.07E+00 5.11E+00 5.24E+00 4.43E+00 4.88E+00 4.84E+00 4.79E+00 (log(poise)) Log IVc 2.17E−01 1.61E−01 1.70E−01 1.01E−02 n/a 2.17E−01 2.05E−01 (log(dL/g)) S_(h) 2.84E−01 5.93E−01 6.79E−01 6.30E−01 n/a 5.60E−02 6.17E−02 (dimensioness) S_(v) 5.96E−02 1.24E−01 1.43E−01 1.32E−01 n/a 1.18E−02 1.30E−02 (dimensionless) LCBF 8.45E−03 3.68E−02 4.84E−02 4.17E−02 n/a 3.30E−04 4.00E−04 (dimensionless)

TABLE 3 Long Chain Branching Factor (LCBF) of Comparative ethylene polymers: Comparatives A-C and Comparatives D-G. Comp. A Comp. B Comp. C Comp. D Comp. E Comp. F Comp. G Mv (g/mole) 8.79E+04 8.94E+04 8.70E+04 9.75E+04 1.02E+05 1.04E+05 9.76E+04 [η] (dL/g) 1.300 1.314 1.293 1.441 1.488 1.507 1.448 Mw/Mn 1.88 1.80 1.89 3.04 2.85 2.79 2.89 A 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 SCB 23.2 23.3 23.4 14.2 13.7 14.1 15.1 (CH₃#/1000C) ZSV (poise) 1.51E+05 1.51E+05 1.53E+05 1.56E+05 1.43E+05 1.55E+05 1.35E+05 Log ZSV_(c) 5.20E+00 5.22E+00 5.21E+00 5.03E+00 5.02E+00 5.06E+00 4.99E+00 (log(poise)) Log IVc 1.74E−01 1.79E−01 1.72E−01 1.95E−01 2.08E−01 2.15E−01 2.00E−01 (log(dL/g)) S_(h) 6.22E−01 6.14E−01 6.35E−01 3.51E−01 2.76E−01 2.90E−01 2.87E−01 (dimensionless) S_(v) 1.31E−01 1.29E−01 1.33E−01 7.38E−02 5.81E−02 6.09E−02 6.03E−02 (dimensionless) LCBF 4.06E−02 3.96E−02 4.23E−02 1.30E−02 8.03E−03 8.83E−03 8.65E−03 (dimensionless) Ti (ppm) 0.33 ± 0.013^(a) 1.5 2.2 2.2 2.0 Hf (ppm) ^(b) ^(b) ^(b) ^(b) ^(b) Internal 0.006 0.006 0.006 0.004 0.004 0.004 0.004 Unsaturations/100C Side Chain 0.001 0.025 0.025 0.002 0.003 0.002 0.004 Unsaturations/100C Terminal 0.008 0.007 0.007 0.025 0.020 0.021 0.03 Unsaturations/100C ^(a)average of AFFINITY (3 samples, but not Comp. A-C); via Neutron Activation Analysis (N.A.A.) ^(b)undetectable via Neutron Activation Analysis

TABLE 4A Continuous solution process catalyst parameters for Examples 50 through 52 and Comparatives 60 and 61 Process Parameter Example 50 Example 51 Example 52 Comp. 60 Comp. 61 Reactor Mode Series Series Parallel Series Parallel R1 Catalyst^(a) CpF-1 CpF-2 CpF-2 PIC-2 PIC-1 (component A, or component C) R2 Catalyst^(b) PIC-1 PIC-1 PIC-1 PIC-2 PIC-1 R1 catalyst (ppm) 0.72 0.40 0.44 0.14 0.26 R1 ([M^(c)]/[A]) or 122 45 45 100 65 R1 ([M]/[C]) mole ratio R1 ([P^(d)]/[M]) mole ratio 0.40 0.15 0.15 0.5 0.30 R1 ([B^(e)]/[A]) or 1.47 1.21 1.21 1.2 1.20 R1 ([B]/[C]) mole ratio R2 catalyst (ppm) 0.15 0.17 0.59 0.38 0.27 R2 ([M^(c)]/[C]) mole ratio 25 25 65 30 65 R2 ([P^(d)]/[M]) mole ratio 0.30 0.30 0.30 0.5 0.30 R2 ([B^(e)]/[C]) mole ratio 1.50 1.50 1.50 1.5 1.50 Prod. Rate (kg/h) 64.1 64.4 60.2 76.7 49.5 ^(a)Catalysts: CpF-1 = [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂]: CpF-2 = [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂]; PIC-1 = [Cp[(t-Bu)₃PN]TiCl₂], and; PIC-2 = [Cp[(isopropyl)₃PN]TiCl₂]. ^(b)in-line Ziegler-Natta catalyst formulation ^(c)methylaluminoxane (MMAO-7) ^(d)2,6-di-tert-butyl-4-ethylphenol ^(e)trityl tetrakis(pentafluoro-phenyl)borate

TABLE 4B Continuous solution process catalyst parameters for Examples 50 through 52 and Comparatives 60 and 61. Process Parameter Example 50 Example 51 Example 52 Comp. 60 Comp. 61 R3 volume (L) 2.2 2.2 2.2 2.2 2.2 ES^(R1) (%) 50.0 50.0 60.0 50.0 70 ES^(R2) (%) 50.0 50.0 40.0 50.0 30 ES^(R3) (%) 0.0 0.0 0.0 0.0 0.0 R1 ethylene 8.6 9.8 11.1 9.1 8.3 concentration (wt %) R2 ethylene 12.3 12.3 12.4 13.4 13.0 concentration (wt %) R3 ethylene 12.3 12.3 12.4 13.4 13 concentration (wt %) ((1-octene)/ 0.400 0.41 0.4 0.75 1.16 (ethylene))^(R1) (wt/wt) ((1-octene)/ 0.00 0.00 0.00 0.00 0.00 (ethylene))^(R2) (wt/wt) (1-octene/ethylene) 0.200 0.205 0.240 0.37 0.817 (wt/wt) (total) OS^(R1) (%) 100 100 100 100 100 OS^(R2) (%) 0 0 0 0 0 OS^(R3) (%) 0 0 0 0 0 H₂ ^(R1) (ppm) 5.35 5.35 7.21 0.5 0.4 H₂ ^(R2) (ppm) 0.5 0.5 0.54 0.5 0.47 H₂ ^(R3) (ppm) 0.0 0.0 0.0 0.0 0.0

TABLE 4C Continuous solution process catalyst parameters for Examples 50 through 52 and Comparatives 60 and 61. Process Parameter Example 50 Example 51 Example 52 Comp. 60 Comp. 61 R1 total solution rate 393.3 345.1 344 439.0 392.2 (kg/h) R2 total solution rate 156.7 204.9 344 160.2 107.8 (kg/h) R3 solution rate (kg/h) 0 0 0 0 0 Total solution rate 550 550 688 600 500 (kg/h) R1 feed inlet temp (° C.) 30 30 30 30 35 R2 feed inlet temp (° C.) 50 50 50 30 54.9 R3 feed inlet temp (° C) NA 131 131 130 130 R1 catalyst inlet temp 145.1 21.4 24.5 32.2 29.9 (° C.) R2 catalyst inlet temp 41.7 30.4 30.4 31.1 40.3 (° C.) R1 Mean temp (° C.) 131.8 139.5 154.4 141.0 138.3 R2 Mean temp (° C.) 189.9 189.8 196.0 191.0 195.4 R3 exit temp (° C.) 192.7 191.1 180.6 193.0 162.6 Q^(R1) (%) 80.0 80.6 80.0 89 89.0 Q^(R2) (%) 85.0 85.0 94.0 79 96.2 Q^((R2+R3)) (%) 86.3 86.6 NA 81.5 NA Q^(R3) (%) 8.5 10.4 38.1 12 27.26 Q^(T) (%) 91.8 92.0 90.8 89.7 93.4

TABLE 5 Physical properties of Examples and Comparatives. Physical Property Example 50 Example 51 Example 52 Comp. 60 Comp. 61 Comp. 67 Density (g/cc) 0.9181 0.9172 0.9172 0.9162 0.9193 0.9162 Melt Index, I₂ 1.02 1.06 0.92 0.96 0.99 0.99 (dg/min) Stress Exponent 1.46 1.45 1.39 1.30 1.18 1.27 I₁₀/I₂ 10.2 9.91 8.80 7.67 6.22 7.59 MFR, I₂₁/I₂ 43.7 41.9 30.7 28.5 19.7 30.8 SEC, M_(w) 96695 96238 93004 94536 99753 102603 SEC, M_(w)/M_(n) 2.86 2.65 2.04 2.88 2.37 3.08 SEC, M_(z)/M_(w) 2.12 2.14 1.67 2.15 1.86 2.32 CDBI₅₀ 8.0 6.6 55.4 92.1 62.6 77.5 Branch Freq. 16.1 15.8 16.2 13.5 12.1 14.6 (C₆/1000C) Comonomer 3.2 3.2 3.2 2.7 2.4 2.9 mole % Ti (ppm) n/a 0.127 0.208 0.303 ± 0.056^(a) Hf (ppm) n/a 0.530 0.624 Undetectable^(a) Al (ppm) n/a 4.42 9.05 6.56 ± 1.40^(a) Mg (ppm) n/a 0.165 0.286 0.160 ± 0.089^(a) Cl (ppm) n/a 0.370 0.503 0.496 ± 0.038^(a) Internal 0.012 0.012 0.016 0.018 0.020 0.021 Unsaturation/100C Side Chain 0.003 0.002 0.003 0.003 0.000 0.002 Unsaturation/100C Terminal 0.005 0.005 0.006 0.007 0.006 0.006 Unsaturation/100C ^(a)database average, historical catalyst residues unbridged single site catalyst formulation

TABLE 6A Continuous solution process catalyst parameters for Examples 58 and 59. Process Parameter Example 58 Example 59 Reactor Mode Series Series R1 Catalyst^(a) (component A) CpF-1 CpF-1 R2 Catalyst^(b) PIC-1 PIC-1 R1 catalyst (ppm) 1.08 0.97 R1 ([M^(c)]/[A]) mole ratio 136.0 136.1 R1 ([P^(d)]/[M]) mole ratio 0.40 0.40 R1 ([B^(e)]/[A]) mole ratio 1.80 1.80 R2 catalyst (ppm) 0.31 1.32 R2 ([M^(c)]/[C]) mole ratio 30.01 25.00 R2 ([P^(d)]/[M]) mole ratio 0.30 0.30 R2 ([B^(e)]/[C]) mole ratio 1.28 1.27 Prod. Rate (kg/h) 89.7 70.6 ^(a)Catalysts: CpF-1 = [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂]: CpF-2 = [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂]; PIC-1 = [Cp[(t-Bu)₃PN]TiCl₂], and; PIC-2 = [Cp[(isopropyl)₃PN]TiCl₂]. ^(b)in-line Ziegler-Natta catalyst formulation ^(c)methylaluminoxane (MMAO-7) ^(d)2,6-di-tert-butyl-4-ethylphenol ^(e)trityl tetrakis(pentafluoro-phenyl)borate

TABLE 6B Continuous solution process catalyst parameters for Examples 58 and 59. Process Parameter Example 58 Example 59 R3 volume (L) 2.2 2.2 ES^(R1) (%) 30 45 ES^(R2) (%) 70 55 ES^(R3) (%) 0 0 R1 ethylene concentration (wt %) 8.83 10.18 R2 ethylene concentration (wt %) 15.02 14.67 R3 ethylene concentration (wt %) 15.02 14.67 ((1-octene)/(ethylene))^(R1) (wt/wt) 0.33 0.02 OS^(R1) (%) 50 100 OS^(R2) (%) 50 0 OS^(R3) (%) 0 0 H₂ ^(R1) (ppm) 0.22 0.75 H₂ ^(R2) (ppm) 30.04 29.99 H₂ ^(R3) (ppm) 0 0

TABLE 6C Continuous solution process catalyst parameters for Examples 58 and 59. Process Parameter Example 58 Example 59 R1 total solution rate (kg/h) 268.9 175.6 R2 total solution rate (kg/h) 268.9 175.6 R3 solution rate (kg/h) 0 0 Total solution rate (kg/h) 537.8 351.2 R1 feed inlet temp (° C.) 30.01 29.82 R2 feed inlet temp (° C.) 29.97 28.88 R3 feed inlet temp(° C.) NA NA R1 catalyst inlet temp (° C.) 145 145 R2 catalyst inlet temp (° C.) 30 30 R1 Mean temp (° C.) 135.7 151.9 R2 Mean temp (° C.) 206.1 211.3 Q^(R1) (%) 87.90 91.62 Q^(R2) (%) 81.99 88.07 Q^((R2+R3)) (%) 85.72 90.62

TABLE 7 Physical properties of Examples 58 and 59. Physical Property Example 58 Example 59 Density (g/cc) 0.9283 0.9440 Melt Index, I₂ (dg/min) 4.03 0.24 Stress Exponent 1.85 1.95 I₁₀/I₂ 21.12 n/a MFR, I₂₁/I₂ 142 215.76 SEC, M_(w) 72126 119964 SEC, M_(w)/M_(n) 6.23 10.41 SEC, M_(z)/M_(w) 3.68 3.89 CDBI₅₀ 41.1 n/a Branch Freq. (C₆/1000 C) 12.6 4.6 Comonomer 2.5 0.9 mole % Internal Unsaturation/1000 0.010 n/a Side Chain Unsaturation/100 C 0.006 n/a Terminal Unsaturation/100 C 0.009 n/a

TABLE 8 Physical attributes of the first, second and third ethylene interpolymer in Example 51, relative to Comparative 67. Physical Reactor 1 Reactor 2 Reactor 3 Example Attribute 1^(st) Interpoly 2^(nd) Interpoly 3^(rd) Interpoly 51 Example 51 Weight   49.7   45.3 5.0% 100 Percent (%) M_(n)  72856 21935 21935 36278 M_(w) 141247 39575 39575 96238 Polydispersity    1.94   1.80 1.80 2.65 (M_(w)/M_(n)) BrF (#C₆/   30.3 ^(a)   1.48 ^(g) 1.48 15.8 1000 C) CDBI₅₀ (%) 85-90 80-95 80-95 6.6 (range) Density (g/cm³)    0.8940 ^(b)   0.9413 ^(f) 0.9413 0.9172 Melt Index    0.1 ^(c)   33.9 ^(c) 33.9 1.06 (dg/min) LCBF    0.0740 ^(d) ^(e) ^(e) 0.0368 (dimensionless) Comparative 67 Weight   47.1   47.9   5% 100 Percent (%) M_(n)  48956 20045 20045 33358 M_(w) 165552 35917 25917 102603 Polydispersity    1.95   1.79 1.79 3.08 (M_(w)/M_(n)) BrF (#C₆/   12.7 ^(a)   16.3 ^(g) 16.3 14.6 1000 C) CDBI₅₀ (%) 85-97 80-95 80-95 77.5 (range) Density (g/cm³)    0.9141 ^(b)   0.9181 ^(f) 0.9181 0.9162 Melt Index    0.05 ^(c)   49.2 ^(c) 49.2 0.99 (dg/min) LCBF ^(e) ^(e) ^(e) ^(e) (dimensionless) ^(a) BrF (#C₆/1000 C) = 120.32807-2.1647891(T^(P) _(CTREF))/0.0118658(T^(P) _(CTREF))²-0.000022(T^(P) _(CTREF))³; where T^(P) _(CTREF) is the peak elution temperature of the first ethylene interpolymer in the CTREF chromatogram. ^(b) BrF (#C₆/1000 C) = 9341.8 (ρ¹)² − 17766 (ρ¹) + 8446.8, where ρ¹ was the density of the first ethylene interpolymer. ^(c) Melt Index (I₂, dg/min) = 5000[1 + (5.7e−5 × Mw)^(2.0)]^(((−4.5-1)/2.0)) + 1.0e−6 where Mw is the Mw of each slice of a MWD with a weight defined by a (wt. fraction * sigmoid function); where the sigmoid function = 1/(1 + exp(−(logMw − 4.2)/0.55)) ^(d) 0.0736 = LCBF^(Example 51)/(wt^(R1) _(fr)), where wt^(R1) _(fr) is the weight fraction of the first ethylene interpolymer in Example 51. ^(e) LCBF < 0.0001 (undetectable levels of LCB) ^(f) density of the second and third ethylene interpolymer given the linear specific volume blending rule and ρ¹, ρ^(f) and weight fractions ^(g) BrF(#C6/1000 C) of second and third ethylene interpolymer given linear BrF blending rule and weight fractions

TABLE 9 Blown film processing conditions targeting 1.0 mil (25 μm) film and output rate of 100 lb/hr, Examples 51 and 52, relative to Comparative 67. Process Parameter Units Example 51 Example 52 Comp. 67 Density (g/cm³) 0.9172 0.9172 0.9162 Melt Index, I₂ (dg/min) 1.06 0.92 0.99 Processing Aid^(a) ppm 800 800 800 Output (lbs/hr) lb/hr 100 100 100 Melt Temperature ° F. 423 422 472 Extruder Pressure psi 3215 3465 3818 Extruder Current Amp 30.7 34.2 38 Extruder Voltage Volt 191 182 197 Screw Speed Rpm 40 38 41 Nip Roll Speed ft/min 131 131 131 Frost Line Height In 16 16 16 Specific Output lb/(hr · rpm) 2.5 2.6 2.4 Specific Power lb/(hr · amp) 3.3 2.9 2.7 Specific Energy W/lb/hr 58.6 62.2 74.1 ^(a)800 ppm of FX5920A processing aid (available from 3M, St. Paul, MN, USA)

TABLE 10A Blown film physical properties of Examples and Comparatives; film thickness 1.0 mil (25 μm) unless indicated otherwise. Physical Example Example Comp. Property Units Method 51F 52F 67F Density (g/ ASTM 0.9172 0.9172 0.9162 cm³) D792 Melt Index, (dg/ ASTM 1.06 0.92 0.99 I₂ min) D1238 Film mil Micro- 1.0 1.0 1.0 Thickness meter Film wt % 21 CFR 0.16 0.21 0.46 Hexane §177.1520 Extractables^(a) S.I.T. @ ° C. In-house 93.6 89.1 99.1 4.4N/13 mm^(b) Tack Onset ° C. In-house 90 86 101 @ 1.0N^(b) Max Hot N In-house 3.2 3.62 5.53 Tack Strength^(b) Temperature ° C. In-house 105 100 115 at Max. Hot Tack^(b) Tear MD g/ ASTM 222 288 282 mil D1922 Tear TD g/ ASTM 468 568 507 mil D1922 Dart g/ ASTM 800 449 400 Impact mil D1709 Method A Lubricated J/ In-house 48 75 81 Puncture mm Gloss at 45° ASTM 26 43 46 D2457 Haze % ASTM 32.9 15.9 13.5 D1003 ^(a) = 3.5 mil film (89 μm) ^(b) = 2.0 mil film (51 μm)

TABLE 10B Blown film physical properties of Examples and Comparatives; film thickness 1.0 mil (25 μm) unless indicated otherwise. Physical Example Example Comp. Property Units Method 51F 52F 67F Density (g/ ASTM 0.9172 0.9172 0.9162 cm³) D792 Melt (dg/ ASTM 1.06 0.92 0.99 Index, I₂ min) D1238 Film mil Micro- 1.0 1.0 1.0 Thickness meter 1% Sec MPa ASTM 212 228 164 Modulus MD D882 1% Sec MPa ASTM 255 258 161 Modulus TD D882 2% Sec MPa ASTM 178 190 142 Modulus MD D882 2% Sec MPa ASTM 211 215 137 Modulus TD D882 Tensile Break MPa ASTM 45 48.8 49.7 Str MD D882 Tensile Break MPa ASTM 40.4 48.1 29.5 Str TD D882 Elongation at % ASTM 518 583 548 Break MD D882 Elongation at % ASTM 735 791 665 Break TD D882 Tensile Yield MPa ASTM 10.2 10.5 9.1 Str MD D882 Tensile Yield MPa ASTM 11.4 11.5 8.7 Str TD D882 Tensile Elong % ASTM 10 10 11 at Yield MD D882 Tensile Elong % ASTM 9 9 10 at Yield TD D882 Film ft-lb/ ASTM 1286 1605 1327 Toughness, in³ D882 Total Energy to Break TD Film ft-lb/ ASTM 1528 1870 1105 Toughness, in³ D882 Avg. Total Energy to Break

TABLE 11A Percent (%) improved SEC weight average molecular weight (M_(w)) at a reactor temperature of 130° C. and 90% ethylene conversion for the bridged metallocene catalyst formulation relative to the unbridged single site catalyst formulation. Weight % Bridged Metallocene Unbridged Single Site 1-octene in Catalyst Formulation Catalyst Formulation % ethylene Component M_(w) ^(A) Component M_(w) ^(C) Improved interpolymers A (see¹) C (see²) M_(w) (see³) 0.1 CpF-1 520658 PIC-1 493848 5.4 2.5 CpF-1 216926 PIC-1 165308 31 5.0 CpF-1 179652 PIC-1 130600 38 7.5 CpF-1 160892 PIC-1 113782 41 10.0 CpF-1 148783 PIC-1 103179 44 12.5 CpF-1 140021 PIC-1 95641 46 15.0 CpF-1 133246 PIC-1 89892 48 17.5 CpF-1 127775 PIC-1 85302 50 20.0 CpF-1 123217 PIC-1 81516 51 22.5 CpF-1 119332 PIC-1 78316 52 25.0 CpF-1 115961 PIC-1 75560 53 27.5 CpF-1 112994 PIC-1 73151 54 30.0 CpF-1 110351 PIC-1 71019 55 32.5 CpF-1 107974 PIC-1 69112 56 35.0 CpF-1 105820 PIC-1 67392 57 37.5 CpF-1 103852 PIC-1 65830 58 40.0 CpF-1 102045 PIC-1 64401 58 42.5 CpF-1 100376 PIC-1 63087 59 45.0 CpF-1 98828 PIC-1 61873 60 ¹M_(w) ^(A) = 278325 × (Octene^(wt%))-0.272; where (Octene^(wt%)) is the weight % of octene in the ethylene/1-octene interpolymer ²M_(w) ^(C) = 225732 × (Octene^(wt%))-0.340 ³100% × (M_(w) ^(A)-M_(w) ^(C))/M_(w) ^(C)

TABLE 11B Percent (%) improved SEC weight average molecular weight (M_(w)) at a reactor temperature of 160° C. and 90% ethylene conversion for the bridged metallocene catalyst formulation relative to the unbridged single site catalyst formulation. Weight Bridged Unbridged % 1- Metallocene Single Site octene in Catalyst Catalyst ethylene Formulation Formulation % inter- Component M_(w) ^(A) Component M_(w) ^(C) Improved polymers A (see¹) C (see²) M_(w) (see³) 0.1 CpF-1 293273 PIC-1 248166 18 2.5 CpF-1 130734 PIC-1 91198 43 5.0 CpF-1 109858 PIC-1 73513 49 7.5 CpF-1 99227 PIC-1 64804 53 10.0 CpF-1 92315 PIC-1 59257 56 12.5 CpF-1 87287 PIC-1 55285 58 15.0 CpF-1 83382 PIC-1 52237 60 17.5 CpF-1 80217 PIC-1 49792 61 20.0 CpF-1 77573 PIC-1 47766 62 22.5 CpF-1 75314 PIC-1 46048 64 25.0 CpF-1 73348 PIC-1 44564 65 27.5 CpF-1 71614 PIC-1 43262 66 30.0 CpF-1 70067 PIC-1 42107 66 32.5 CpF-1 68673 PIC-1 41072 67 35.0 CpF-1 67408 PIC-1 40136 68 37.5 CpF-1 66251 PIC-1 39284 69 40.0 CpF-1 65186 PIC-1 38504 69 42.5 CpF-1 64202 PIC-1 37784 70 45.0 CpF-1 63287 PIC-1 37119 70 ¹M_(w) ^(A) = 164540 × (Octene^(wt%))-0.251; where (Octene^(wt%)) is the weight % of octene in the ethylene/1-octene interpolymer ²M_(w) ^(C) = 121267 × (Octene^(wt%))-0.311 ³100% × (M_(w) ^(A)-M_(w) ^(C))/M_(w) ^(C)

TABLE 12A Percent (%) improvement (reduction) in (α-olefin/ethylene) weight ratio in the reactor feed, for the bridged metallocene catalyst formulation relative to the unbridged single site catalyst formulation, to produce ethylene interpolymers at the densities shown (130° C. reactor temperature and about 90% ethylene conversion). Bridged Unbridged Metallocene Single Site Weight Catalyst Catalyst % % 1- Formulation Formulation Reduced octene in (α- (α- (α-olefin/ ethylene Com- olefin/ Com- olefin/ ethylene) inter- ponent ethylene)^(A) ponent ethylene)^(C) Ratio polymers A (see¹) C (see²) (see³) 0.0 CpF-1 0.000 PIC-1 0.00 n/a 2.5 CpF-1 0.0075 PIC-1 0.174 −96% 5.0 CpF-1 0.045 PIC-1 0.422 −89% 7.5 CpF-1 0.088 PIC-1 0.690 −87% 10.0 CpF-1 0.136 PIC-1 0.980 −86% 12.5 CpF-1 0.188 PIC-1 1.29 −85% 15.0 CpF-1 0.246 PIC-1 1.62 −85% 17.5 CpF-1 0.309 PIC-1 1.98 −84% 20.0 CpF-1 0.377 PIC-1 2.35 −84% 22.5 CpF-1 0.449 PIC-1 2.75 −84% 25.0 CpF-1 0.527 PIC-1 3.17 −83% 27.5 CpF-1 0.610 PIC-1 3.60 −83% 30.0 CpF-1 0.698 PIC-1 4.06 −83% 32.5 CpF-1 0.790 PIC-1 4.55 −83% 35.0 CpF-1 0.888 PIC-1 5.05 −82% 37.5 CpF-1 0.991 PIC-1 5.57 −82% 40.0 CpF-1 1.10 PIC-1 6.12 −82% 42.5 CpF-1 1.21 PIC-1 6.68 −82% 45.0 CpF-1 1.33 PIC-1 7.27 −82% ¹(α-olefin/ethylene)^(A) = 0.0004 × (Octene^(wt%))² + 0.0121 × (Octene^(wt%)) − 0.0253; where (Octene^(wt%)) is the weight % of octene in the ethylene/1-octene interpolymer ²(α-olefin/ethylene)^(C) = 0.0017 × (Octene^(wt%))² + 0.0862 × (Octene^(wt%)) − 0.0517 ³100% × ((α-olefin/ethylene)^(A) − (α-olefin/ethylene)^(C))/(α-olefin/ethylene)^(C)

TABLE 12B Percent (%) improvement (reduction) in (α-olefin/ethylene) weight ratio in the reactor feed, for the bridged metallocene catalyst formulation relative to the unbridged single site catalyst formulation, to produce ethylene interpolymers at the densities shown (160° C. reactor temperature and about 90% ethylene conversion). Bridged Unbridged Weight Metallocene Single Site % % 1- Catalyst Catalyst Reduced octene in Formulation Formulation (α-olefin/ ethylene (α-olefin/ (α-olefin/ ethylene) inter- Component ethylene)^(A) Component ethylene)^(C) Ratio polymers A (see¹) C (see²) (see³) 0.0 CpF-1 0.00 PIC-1 0.00 n/a 2.5 CpF-1 0.0078 PIC-1 0.183 −96% 5.0 CpF-1 0.031 PIC-1 0.407 −92% 7.5 CpF-1 0.066 PIC-1 0.653 −90% 10.0 CpF-1 0.112 PIC-1 0.920 −88% 12.5 CpF-1 0.170 PIC-1 1.21 −86% 15.0 CpF-1 0.238 PIC-1 1.52 −84% 17.5 CpF-1 0.318 PIC-1 1.85 −83% 20.0 CpF-1 0.409 PIC-1 2.20 −81% 22.5 CpF-1 0.512 PIC-1 2.57 −80% 25.0 CpF-1 0.625 PIC-1 2.97 −79% 27.5 CpF-1 0.750 PIC-1 3.39 −78% 30.0 CpF-1 0.886 PIC-1 3.82 −77% 32.5 CpF-1 1.03 PIC-1 4.28 −76% 35.0 CpF-1 1.19 PIC-1 4.76 −75% 37.5 CpF-1 1.36 PIC-1 5.26 −74% 40.0 CpF-1 1.54 PIC-1 5.78 −73% 42.5 CpF-1 1.74 PIC-1 6.33 −73% 45.0 CpF-1 1.94 PIC-1 6.89 −72% ¹(α-olefin/ethylene)^(A) = 0.0009 × (Octene^(wt%))² + 0.0027 × (Octene^(wt%)) − 0.0046; where (Octene^(wt%)) is the weight % of octene in the ethylene/1-octene interpolymer ²(α-olefin/ethylene)^(C) = 0.0017 × (Octene^(wt%))² + 0.0771 × (Octene^(wt%)) − 0.0208 ³100% × ((α-olefin/ethylene)¹-(α-olefin/ethylene)^(C)/(α-olefin/ethylene)^(C)

TABLE 13 CPU continuous solution phase, one reactor, ethylene homopolymerization using the bridged metallocene catalyst formulation. Polymerization Temp. (° C.) 130 160 190 Sample Code Example C1 Example C2 Example C3 Example C4 Example C5 Example C6 Component A¹ 0.15 0.47 0.19 0.82 0.22 0.93 Concentration in Reactor [mM/L] ([M]/[A]) 100 100 100 100 100 100 mole ratio ([P]/[M]) 0.40 0.40 0.40 0.40 0.40 0.40 mole ratio ([B]/[A]) 1.20 1.20 1.20 1.20 1.20 1.20 mole ratio HUT^(CPU) (min) 119 119 109 109 99 99 Q^(CPU) (%) 74.5 94.2 74.9 94.4 75.5 94.8 K_(p) ^(CPU) 12731 22328 11727 15704 13116 17761 (L/(mM · min) ¹CpF-2 = [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂]

TABLE 14 13C-NMR determined long chain branching (LCB) in the first ethylene interpolymer (ethylene homopolymer) produced using the bridged metallocene catalyst formulation¹ on the CPU. Sample Example C10 Example C11 Example C12 Example C13 Example C14 Example C15 CPU Reactor 190 190 160 160 130 130 Temp. (° C.) CPU Ethylene 95.6 85.3 95.0 75.3 93.6 85.1 Conversion (wt %) CPU [ethylene] 0.62 2.10 0.57 2.80 0.53 1.23 out (wt. %) ¹³C LCB/1000C 0.23 0.09 0.09 0.03 0.07 0.03 GPC M_(w) (g/mol) 46337 93368 107818 255097 234744 305005 Pd (M_(w)/M_(n)) 1.88 1.88 1.85 1.9 2.02 2.29 ¹³C-NMR, 2.37 1.68 1.64 0.98 0.94 0.73 C1/10000 ¹³C-NMR, 0.2 0.14 0.17 0.10 0.12 0.09 C2/1000C ¹³C-NMR, 0.08 0.05 0.05 D² D D C3/1000C ¹³C-NMR, 0.07 0.05 0.05 D D D C4/1 000C ¹³C-NMR, 0.3 0.12 0.12 D 0.07 D (C6 + LCB)/ 1000C ¹³C-NMR, 1.1 0.52 0.47 0.22 0.23 0.21 Sat.Term./1000C M_(n) (g/mol) 24640 49615 58131 118329 116035 133001 M_(z) (g/mol) 73219 152320 176254 383637 447833 567658 I₂ (dg/min) 16.6 n/a 0.15 n/a n/a n/a I₂₁ (dg/min) 380 n/a 10 0.54 0.53 0.12 I₂₁/I₂ 22.9 n/a 66.1 n/a n/a n/a ¹Component A = [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂] D = detectable but not quantifiable 

What is claimed is:
 1. A continuous solution polymerization process comprising: i) injecting ethylene, a process solvent, a first homogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen into a first reactor to produce a first exit stream comprising a first ethylene interpolymer in the process solvent; ii) passing the first exit stream into a second reactor and injecting into the second reactor, ethylene, the process solvent, a second homogeneous catalyst formulation, optionally one or more .alpha.-olefins and optionally hydrogen to produce a second exit stream comprising a second ethylene interpolymer and the first ethylene interpolymer in the process solvent; and iii) passing the second exit stream into a third reactor and optionally injecting into the third reactor, ethylene, a process solvent, one or more .alpha.-olefins, hydrogen, a third homogeneous catalyst formulation, under a heterogeneous catalyst formulation, or a combination thereof to produce a third exit stream comprising a third ethylene interpolymer, the second ethylene interpolymer and the first ethylene interpolymer in the process solvent; wherein, the continuous solution polymerization process comprises one or more of the following: (I) at least a 70% reduced α-olefin/ethylene] weight ratio as defined by the following formula: ${\%\mspace{14mu}{{Reduced}\mspace{14mu}\left\lbrack \frac{\alpha - {olefin}}{ethylene} \right\rbrack}} = {{100 \times \left\{ \frac{\left( \frac{\alpha - {olefin}}{ethylene} \right)^{A} - \left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}}{\left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}} \right\}} \leq {{- 70}\%}}$ wherein (α-olefin/ethylene)^(A) is calculated by dividing the weight of the α-olefin added to the first reactor by the weight of the ethylene added to the first reactor, wherein the first ethylene interpolymer having a target density is produced by the first homogeneous catalyst formulation, and (α-olefin/ethylene)^(C) is calculated by dividing the weight of the α-olefin added to the first reactor by the weight of the ethylene added to the first reactor, wherein a control ethylene interpolymer having the target density is produced by replacing the first homogeneous catalyst formulation with a fourth homogeneous catalyst formulation; and (II) at least a 5% improved weight average molecular weight as defined by the following formula: % Improved M _(w)=100%×(M _(w) ^(A) −M _(w) ^(C))/M _(w) ^(C) wherein Mw^(A) is a weight average molecular weight of the first ethylene interpolymer and Mw^(C) is a weight average molecular weight of a comparative ethylene interpolymer; wherein the comparative ethylene interpolymer is produced in the first reactor by replacing the first homogeneous catalyst formulation with the third homogeneous catalyst formulation.
 2. The process according to claim 1 further comprising: a) adding a catalyst deactivator A to the second exit stream, downstream of the second reactor, forming a deactivated solution A; or adding a catalyst deactivator B to the third exit stream, downstream of the third reactor, forming a deactivated solution B; and b) phase separating deactivated solution A or deactivated solution B to recover the ethylene interpolymer product.
 3. The process according to claim 2, further comprising: c) adding a passivator to deactivated solution A or deactivated solution B forming a passivated solution, with the proviso that step c) omitted if the heterogeneous catalyst formulation is not added to the third reactor, and d) phase separating said-deactivated solution A or deactivated solution B, or the passivated solution, to recover the ethylene interpolymer product.
 4. The process according to claim 3, wherein the first homogeneous catalyst formulation is a bridged metallocene catalyst formulation comprising: (a) a component A of Formula (I):

wherein: M is a metal selected from Ti, Hf, or Zr, G is selected from C, Si, Ge, Sn, or Pb, X represents a halogen atom, R⁶, at each occurrence is independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical, these radicals may be linear, branched or cyclic or further substituted with a halogen atom, C₁₋₁₀ alkyl radicals, C₁₋₁₀ alkoxy radicals, C₆₋₁₀ aryl, or aryloxy radicals, R₁ represents a hydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, or a C₆₋₁₀ aryl oxide radical, R₂ and R₃ are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, or a C₆₋₁₀ aryl oxide radical, and R₄ and R₅ are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbyl radial, a C₁₋₂₀ alkoxy radical, or a C₆₋₁₀ aryl oxide radical; b) a component M^(A), comprising an alumoxane co-catalyst; c) a component B^(A), comprising a boron ionic activator; and d) optionally, a component P^(A), comprising a hindered phenol.
 5. The process according to claim 4, having the following molar ratios in the first reactor: component B^(A) to component A from about 0.3:1 to about 10:1;component M^(A) to component A from about 1:1 to about 300:1; and optional component P^(A) to component M^(A) from 0.0:1 to about 1:1.
 6. The process according to claim 5, wherein component M^(A) is methylalumoxane (MMAO-7).
 7. The process according to claim 5, wherein component B^(A) is trityl tetrakis (pentafluoro-phenyl) borate.
 8. The process according to claim 5, wherein component P^(A) is 2,6-di-tert-butyl-4-ethylphenol.
 9. The process according to claim 5, further comprising the injection of the bridged metallocene catalyst formulation into the first reactor at a catalyst inlet temperature from about 20° C. to about 70° C.; and optionally, the component M^(A) and the component P^(A) may be deleted from the bridged metallocene catalyst formulation and replaced with a component J defined by the formula Al(R¹)_(n)(OR²)₀, wherein: R¹, at each occurrence is independently selected from a hydrocarbyl group having from 1 to 10 carbon atoms; OR², at each occurrence, is selected from alkoxy or aryloxy groups, wherein R² is a hydrocarbyl group having from 1 to 10 carbon atoms bonded to oxygen; and (n+o)=3, with the proviso that n is greater than
 0. 10. The process according to claim 5, further comprising the injection of the bridged metallocene catalyst formulation into the first reactor at a catalyst inlet temperature from about 80° C. to about 180° C.
 11. The process according to claim 4, wherein the second homogeneous catalyst formulation is an unbridged single site catalyst formulation comprising: a) a component C defined the Formula (II): (L ^(A))_(a) M(PI)_(b)(Q)_(n)  (II) wherein: M is a metal selected from titanium, hafnium and zirconium; L^(A) is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; P1 is a phosphinimine ligand; Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C₁₋₁₀ hydrocarbyl radical, a C₁₋₁₀ alkoxy radical and a C₅₋₁₀ aryl oxide radical; wherein each of the hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted or further substituted by a halogen atom, a C₁₋₁₈ alkyl radical, a C₁₋₈ alkoxy radical, a C₆₋₁₀ aryl or aryloxy radical, an amido radical which is unsubstituted or substituted by up to two C₁₋₈ alkyl radicals or a phosphido radical which is unsubstituted or substituted by up to two C₁₋₈ alkyl radicals; and a is 1; b is 1; n is 1 or 2, and (a+b+n) is equivalent to the valence of the metal M; b) a component M^(C) comprising an alumoxane co-catalyst; c) a component B^(C) comprising a boron ionic activator; and d) optionally, a component P^(C) comprising a hindered phenol.
 12. The process according to claim 11 having the following molar ratios in the second reactor: component B^(C) to component C from about 0.3:1 to about 10:1; component M^(C) to component C from about 1:1 to about 1000:1; and optional component P^(C) to component M^(C) from 0.0:1 to about 1:1.
 13. The process according to claim 12, wherein component M^(C) is methylalumoxane (MMAO-7).
 14. The process according to claim 12, wherein component B^(C) is trityl tetrakis (pentafluoro-phenyl) borate.
 15. The process according to claim 12, wherein component P^(C) is 2,6-di-tert-butyl-4-ethylphenol.
 16. The process according to claim 12, further comprising the injection of the unbridged single site catalyst formulation into the second reactor at a catalyst inlet temperature from about 20° C. to about 70° C.; and optionally, the component M^(C) and the component P.sup.C may be deleted from the unbridged single site catalyst formulation and replaced with a component J defined by the formula Al(R¹)_(n)(OR²)₀, wherein: R¹ at each occurrence is independently selected from a hydrocarbyl group having from 1 to 10 carbon atoms; OR² at each occurrence, is selected from alkoxy or aryloxy groups, wherein R² is a hydrocarbyl group having from 1 to 10 carbon atoms bonded to oxygen; and (n+o)=3, with the proviso that n is greater than
 0. 17. The process according to claim 11, wherein the third homogeneous catalyst formulation is the bridged metallocene catalyst formulation, the unbridged single site catalyst formulation or a fourth homogeneous catalyst formulation.
 18. The process according to claim 17, wherein the fourth homogeneous catalyst formulation comprises a bulky metal-ligand complex that is not defined by Formula (I) or Formula (II).
 19. The process according to claim 3, wherein the heterogeneous catalyst formulation is an in-line Ziegler-Natta catalyst formulation.
 20. The process according to claim 19, wherein the in-line Ziegler-Natta catalyst formulation is formed in an in-line process comprising: i) forming a first product mixture in an in-line heterogeneous catalyst assembly by combining a stream S1 and a stream S2 and allowing the first product mixture to equilibrate for a HUT-1 seconds; wherein the stream Si comprises a magnesium compound and an aluminum alkyl in the process solvent and the stream S2 comprises a chloride compound in the process solvent; ii) forming a second product mixture in the in-line heterogeneous catalyst assembly by combining the first product mixture with a stream S3 and allowing the second product mixture to equilibrate for a HUT-2 seconds; wherein the stream S3 comprises a metal compound in the process solvent; iii) forming the in-line Ziegler-Natta catalyst formulation in the in-line heterogeneous catalyst assembly by combining the second product mixture with a stream S4 and allowing the in-line Ziegler-Natta catalyst formulation to equilibrate for a HUT-3 seconds prior to injection into the third reactor, wherein the stream S4 comprises an alkyl aluminum co-catalyst in the process solvent; iv) optionally, step iii) is omitted and the in-line Ziegler-Natta catalyst formulation is formed inside the third reactor; wherein, the second product mixture is equilibrated for an additional HUT-3 seconds and injected into the third reactor and the stream S4 is independently injected into the third reactor.
 21. The process according to claim 20, wherein the HUT-1 is from about 5 seconds to about 70 seconds, the HUT-2 is from about 2 seconds to about 50 seconds, and the HUT-3 is from about 0.5 to about 15 seconds; wherein the in-line Ziegler-Natta catalyst formulation and optionally the second product mixture are injected at a catalyst inlet temperature from about 20° C. to about 70° C.
 22. The process according to claim 20, wherein: i) the magnesium compound is defined by the formula Mg(R¹)₂, wherein the R¹ groups may be the same or different; ii) the aluminum alkyl is defined by the formula Al(R³)₃, wherein the R³ groups may be the same or different; iii) the chloride compound is defined by the formula R²Cl; iv) the metal compound is defined by the formulas M(X)_(n) or MO(X)_(n), wherein M represents titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, or a mixture thereof, O represents oxygen, X represents chloride or bromide, and n is an integer that satisfies the oxidation state of the metal M, and; v) the alkyl aluminum co-catalyst is defined by the formula Al(R⁴)_(p)(OR⁵)_(q)(X)_(r), wherein the R⁴ groups may be the same or different, the OR⁵ groups may be the same or different, and (p+q+r)=3, with the proviso that p is greater than 0; wherein R¹, R², R³, R⁴, and R⁵ represent hydrocarbyl groups having from 1 to 10 carbon atoms; optionally R² may be a hydrogen atom.
 23. The process according to claim 22, wherein M in the metal compound is titanium, zirconium, hafnium, vanadium, chromium, or a mixture thereof.
 24. The process according to claim 22, wherein: the molar ratio of the aluminum alkyl to the magnesium compound in the third reactor is from about 3.0:1 to about 70:1; the molar ratio of the chloride compound to the magnesium compound in the third reactor is from about 1.0:1 to about 4.0:1; the molar ratio of the alkyl aluminum co-catalyst to the metal compound in the third reactor is from about 0:1 to about 10:1; and the molar ratio of the aluminum alkyl to the metal compound in the third reactor is from about 0.05:1 to about 2:1.
 25. The process according to claim 3, wherein the heterogeneous catalyst formulation is a batch Ziegler-Natta catalyst formulation.
 26. The process according to claim 25 wherein the batch Ziegler-Natta catalyst formulation is formed in a batch process comprising: i) forming the batch Ziegler-Natta catalyst formulation by combining a stream S5 and a stream S4 and injecting the batch Ziegler-Natta catalyst formulation into the third reactor, wherein the stream S4 comprises an alkyl aluminum co-catalyst in the process solvent and stream S5 comprises a batch Ziegler-Natta procatalyst in the process solvent; ii) optionally, step i) is skipped and the batch Ziegler-Natta catalyst formulation is formed inside the third reactor by independently injecting the stream S4 and said stream S5 into the third reactor; wherein, the batch Ziegler-Natta catalyst formulation or the streams S4 and the stream S5 are injected into the third reactor at a temperature from about 20° C. to about 70° C.
 27. The process according to claim 26, wherein the alkyl aluminum co-catalyst is defined by the formula Al(R⁴)_(p)(OR⁵)_(q)(X)_(r), wherein the R⁴ groups may be the same or different, the OR⁵ groups may be the same or different and (p+q+r)=3, with the proviso that p is greater than 0; wherein R⁴ and R⁵ represent hydrocarbyl groups having from 1 to 10 carbon atoms.
 28. The process according to claim 26, wherein the batch Ziegler-Natta procatalyst comprises: i) a magnesium compound defined by the formula Mg(R²)₂, wherein the R¹ groups may be the same or different; ii) a chloride compound defined by the formula R²Cl; iii) optionally an aluminum alkyl halide defined by the formula (R⁶)_(v)AlX_(3-v) wherein the R⁶ groups may be the same or different, X represents chloride or bromide, and v is 1 or 2; and iv) a metal compound defined by the formulas M(X)_(n) or MO(X)_(n), wherein M represents titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium or a mixture thereof, 0 represents oxygen, X represents chloride or bromide, and n is an integer that satisfies the oxidation state of the metal M; and wherein R¹, R², and R⁶, at each occurrence, is a hydrocarbyl group having from 1 to 10 carbon atoms; optionally R² may be a hydrogen atom.
 29. The process according to claim 28, wherein M in the metal compound is titanium, zirconium, hafnium, vanadium, chromium or a mixture thereof.
 30. The process according to claim 28, wherein: the molar ratio of the chloride compound to the magnesium compound in the batch Ziegler-Natta procatalyst is from about 2:1 to about 3:1; the molar ratio of the magnesium compound to the metal compound in the procatalyst is from 5:1 to about 10:1; the molar ratio of the aluminum alkyl halide to the magnesium compound in the procatalyst is from about 0:1 to about 0.5; and; the molar ratio of the alkyl aluminum co-catalyst to the metal compound in the procatalyst is from about 0.5:1 to about 10:1.
 31. The process according to claim 3, wherein the process solvent is one or more C₅ to C₁₂ alkanes.
 32. The process according to claim 3, wherein the first, second and third reactors operate at a temperature from about 80° C. to about 300° C. and a pressure from about 3 MPag to about 45 MPag.
 33. The process according to claim 3, wherein the process solvent in the first reactor has an average reactor residence time from about 10 seconds to about 600 seconds and the process solvent in the second reactor has an average reactor residence time from about 10 seconds to about 720 seconds.
 34. The process according to claim 3, wherein the reactor temperature difference (T^(R2)-T^(R1)) ranges from about 1° C. to about 120° C.; wherein T^(R2) is the temperature of the solution in the second reactor and T^(R1) is the temperature of the solution in the first reactor.
 35. The process according to claim 3, wherein the optional one or more α-olefins are C₃ to C₁₀ α-olefins.
 36. The process according to claim 3, wherein the optional .alpha.-olefin is 1-hexene or 1-octene or a mixture of 1-hexene and 1-octene.
 37. An ethylene interpolymer product produced according to the process according to claim 3, wherein the ethylene interpolymer product has a dimensionless Long Chain Branching Factor, LCBF, greater than or equal to about 0.001, from about 0.0015 parts per million (ppm) to about 2.4 ppm of hafnium, and from about 0.006 ppm to about 5.7 ppm of titanium. 